WO2019221584A2 - Ge en couches, son procédé de fabrication, nanofeuille de ge pelée à partir de celui-ci, et électrode la comprenant pour batterie au lithium-ion - Google Patents

Ge en couches, son procédé de fabrication, nanofeuille de ge pelée à partir de celui-ci, et électrode la comprenant pour batterie au lithium-ion Download PDF

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WO2019221584A2
WO2019221584A2 PCT/KR2019/008903 KR2019008903W WO2019221584A2 WO 2019221584 A2 WO2019221584 A2 WO 2019221584A2 KR 2019008903 W KR2019008903 W KR 2019008903W WO 2019221584 A2 WO2019221584 A2 WO 2019221584A2
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layered
crystal structure
space group
nanosheet
trigonal
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Korean (ko)
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WO2019221584A9 (fr
WO2019221584A3 (fr
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심우영
김혜수
이수운
김민정
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연세대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/68—Crystals with laminate structure, e.g. "superlattices"
    • 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
    • H01M4/36—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
    • 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 layered Ge, a method for preparing the same, and a Ge nanosheet peeled from the same. More specifically, unlike the conventional bulk Ge, the present invention has a two-dimensional crystal structure and is excellent in peelability to peel in the form of a nanosheet.
  • the present invention relates to a layered Ge having a wide surface area and excellent ion capacity, a method for preparing the same, a Ge nanosheet peeled from the same, and an electrode for a lithium ion battery including the same.
  • the research on existing 2D materials is based on the top-down method for separating van der Waals bonds with weak interlayer bondability by physical and chemical methods, and the bottom-up method for growing large-area thin films based on vapor deposition. It is becoming.
  • the top-down method since the pristine of the material to be exfoliated must have a two-dimensional layered crystal structure, graphene without band gap, layered metal oxide / nitride with low charge mobility, electron mobility / Research subjects such as transition metal chalcogenides with low electrical conductivity have very limited problems.
  • 2D materials Due to the limitations of previous research methods, 2D materials have been very limitedly studied for materials such as graphene and transition metal chalcogenides. It is limited in that it is not suitable for the development of low-dimensional future materials of a myriad of 3D bulk materials that are not layered.
  • lithium ion batteries have high energy density and are widely used as a power supply device for complex applications such as portable electronic devices and electric vehicles.
  • lithium ions In order to improve the performance of lithium ion batteries, lithium ions must be easily moved and charged. As the discharge is repeated, structural stability of the electrode should be ensured.
  • Ge When using Ge as an electrode material, it has the advantage of having a high theoretical capacity of 1,384 mAh / g, but there is a problem that the ion storage capacity is drastically reduced due to a volume change of 300 to 400% during the insertion and desorption of lithium ions. . Therefore, when the Ge material is manufactured in a low dimensional structure, the structural stability is improved, thereby minimizing the reduction of the ion storage capacity.
  • the present invention has been made in view of the above, and unlike the conventional 3D bulk Ge, it has a two-dimensional crystal structure, has excellent peelability and is easy to peel in the form of a nanosheet, and has a large surface area and excellent ion capacity. It is an object to provide a layered Ge having, a manufacturing method thereof, and a Ge nanosheet peeled therefrom.
  • Another object of the present invention is to provide an electrode for a lithium ion battery having excellent ion storage capacity and minimizing capacity loss, including the layered Ge or Ge nanosheets according to the present invention.
  • the present invention (1) a trigonal crystal having a space group of Rm-3m by cooling a mixture containing Ca powder and Ge powder and cooling at a predetermined temperature reduction rate.
  • the salt is a method for producing a layered Ge represented by the following formula (1):
  • M is any one selected from Sn, Al, and Ga
  • X is any one selected from Cl, F, and I.
  • the solvent may be at least one selected from ethanol, water, acetone and isopropanol.
  • the heat treatment may be performed for 5 to 10 days at 730 ⁇ 830 °C or 2 ⁇ 24 hours at 830 ⁇ 1000 °C.
  • the cooling may be performed at a temperature reduction rate of 3 ⁇ 20 °C / hour.
  • the step (2) is carried out at -40 ⁇ 0 °C to produce a layered Ge having a trigonal crystal structure (space group Rm-3m). Can be.
  • step (2) may be carried out at 15 ⁇ 60 °C to produce a layered Ge having an amorphous crystal structure.
  • the present invention also provides a layered Ge having a trigonal crystal structure in which the amorphous or space group is Rm-3m.
  • the layered Ge having a trigonal crystal structure in which the space group is Rm-3m has an X-ray diffraction diagram obtained by a powder X-ray diffraction method using Cu-K ⁇ rays.
  • the present invention also provides a Ge nanosheet exfoliated from the layered Ge according to the present invention and having an amorphous or triangular symmetric crystal structure.
  • the thickness of the Ge nanosheets may be 100 nm or less.
  • the present invention (1) the layered CaGe 2 and the space group having a trigonal crystal structure having a space group of Rm-3m after quenching the mixture containing the Ca powder and Ge powder Preparing a compound comprising Ge having a cubic crystal structure of Fd-3m, and (2) a salt capable of selectively removing Ca ions contained in the layered CaGe 2 and dissolving the salt.
  • Treating the layered compound with a mixed solution containing a solvent which can be used to form a Ge nanosheet having a trigonal crystal structure of amorphous or space group (Rm-3m), and the space group is Fd-3m It provides a method for producing a Ge nanosheet comprising the step of producing a Ge nanosheet having a monoclinic (cubic) crystal structure.
  • the heat treatment may be performed for 2 to 24 hours at 830 ⁇ 1,000 °C.
  • step (1) may be performed at 10 ⁇ 40 °C.
  • the present invention also relates to a layered Ge having a trigonal crystal structure having an amorphous or space group of Rm-3m, a Ge nanosheet having an amorphous or triangular symmetric crystal structure, and an amorphous or triangular symmetric crystal structure.
  • an electrode for a lithium ion battery including at least one selected from a Ge nanosheet having a Ge nanosheet including a Ge nanosheet having a cubic crystal structure having a cubic crystal structure having a space group of Fd-3m.
  • the layered Ge according to the present invention has a two-dimensional crystal structure, has excellent peelability and is easily peeled off in the form of a nanosheet, and has a large surface area and excellent ion capacity. It is included to implement a lithium ion battery with excellent ion storage capacity and minimized capacity loss.
  • FIG. 1 is a schematic view of a layered Ge manufacturing method according to an embodiment of the present invention.
  • Figure 2 is a photograph of the samples prepared in Ge, Preparation Example 1, Example 1 of Comparative Example 1.
  • Figure 3 is a graph showing the XRD analysis results for the samples prepared in Ge, Preparation Example 1, Example 1 and Example 2 of Comparative Example 1.
  • Figure 4 is a graph showing the Raman spectrum analysis results for the samples prepared in 3D Ge, Preparation Example 1 and Example 1 of Comparative Example 1.
  • 5A is an SEM image of a conventional 3D bulk Ge.
  • 5B is an SEM image of layered CaGe 2 according to an embodiment of the present invention.
  • 5C is an SEM image of a layered Ge in accordance with one embodiment of the present invention.
  • 5D is an SEM image of the sample prepared in Example 1.
  • FIG. 6A is a TEM image of a sample prepared in Example 1.
  • FIG. 6B is a TEM image of a sample prepared in 3D Ge, Preparation Example 1, and Example 1 of Comparative Example 1.
  • FIG. 6B is a TEM image of a sample prepared in 3D Ge, Preparation Example 1, and Example 1 of Comparative Example 1.
  • 6C is a TEM image of layered Ge according to Example 1 and Example 2.
  • FIG. 6C is a TEM image of layered Ge according to Example 1 and Example 2.
  • 6D is a TEM image of a Ge nanosheet according to Example 4.
  • FIG. 8A is an EDS image of layered CaGe 2 according to Preparation Example 2.
  • FIG. 8B is an EDS image for the layered Ge according to Example 1.
  • FIG. 9 is a graph showing the AFM image and analysis results of Ge nanosheets according to an embodiment of the present invention.
  • FIG. 10A is a graph showing charge and discharge curves of the lithium ion battery of Preparation Example 1.
  • FIG. 10A is a graph showing charge and discharge curves of the lithium ion battery of Preparation Example 1.
  • 10B is a graph showing the discharge capacity according to the cycle of the lithium ion battery prepared in Preparation Example 1 and Comparative Preparation Example 1.
  • 10c is a graph showing capacity characteristics according to discharge rates of the lithium ion batteries prepared in Preparation Example 1 and Comparative Preparation Example 1.
  • FIG. 10c is a graph showing capacity characteristics according to discharge rates of the lithium ion batteries prepared in Preparation Example 1 and Comparative Preparation Example 1.
  • the method of manufacturing a layered Ge according to the present invention can produce a bulk Ge of a conventional 3D structure in a two-dimensional structure, and unlike the existing bulk Ge, it is easy to peel, manufacturing a layered Ge having a wide surface area and excellent ion capacity. can do.
  • step (1) the mixture including Ca powder and Ge powder is heat-treated and then cooled to have a trigonal crystal structure having a space group of Rm-3m and a layer type represented by the formula CaGe 2 . Obtain the compound.
  • the mixture may be heat treated after being encapsulated in a reaction vessel, and the inside of the reaction vessel may be maintained in an inert gas atmosphere or a vacuum atmosphere.
  • the material of the reaction vessel may be, for example, alumina, molybdenum, tungsten or quartz, but any material that does not react with the sample and does not break at a high temperature may be used without limitation in the material.
  • the CaGe 2 prepared through step (1) has a 2D crystal structure different from Ge of the 3D crystal structure, and in step (2) described later, a layer is formed by selectively removing Ca ions of the CaGe 2 .
  • Pictographic Ge can be prepared.
  • the heat treatment may be performed for 6 to 24 hours at 830 ⁇ 1,000 °C or for 5 to 10 days at 730 ⁇ 830 °C.
  • CaGe 2 to be produced may have a layered structure, when the heat treatment temperature is 730 ⁇ 830 °C, the layered CaGe 2 to be prepared may be formed of a polycrystalline. When the layered CaGe 2 is a single crystal, the layered CaGe 2 may have better charge mobility than the polycrystal.
  • the heat treatment is performed below 730 ° C., the sintering reaction of the mixture may not be completed, and thus unreacted raw materials may remain, resulting in a decrease in yield of the layered compound prepared. have.
  • the heat treatment is performed in excess of 1,000 ° C, there may be a problem such that the reaction vessel used in the sintering reaction by the evaporation of Ca ions, or the yield of the layered compound produced is lowered.
  • the heat treatment temperature is 830 ⁇ 1,000 °C
  • the heat treatment is performed for less than 2 hours, the sintering reaction of the mixture is not completed, the unreacted raw material may remain, the layered compound prepared accordingly There may be a problem such as a decrease in yield.
  • the heat treatment is performed for more than 24 hours, there is a fear that the manufacturing process time unnecessarily increases.
  • the heat treatment temperature is 730 ⁇ 830 °C
  • the heat treatment is performed less than 5 days, the sintering reaction of the mixture is not completed, the unreacted raw material may remain, the yield of the layered compound prepared accordingly There may be a problem such as deterioration.
  • the heat treatment is performed for more than 10 days, there is a fear that the manufacturing process time unnecessarily increases.
  • the cooling process may vary depending on the temperature of the heat treatment.
  • the cooling may be natural cooling.
  • the cooling may be carried out at a temperature reduction rate of 3 ⁇ 20 °C / hour, through which the heat-treated layered compound can be single crystallized. Cooling at the temperature reduction rate may increase the size of the single crystal of the layered compound prepared. As the size of the single crystal of the layered compound increases, grain boundaries of the particles may decrease, thereby increasing charge mobility, and the aspect ratio of the nanosheet peeled off when the layered compound is peeled off may increase.
  • the temperature reduction rate is less than 3 ° C / hour, a change in the composition of the material produced due to the vaporization of Ca ions may occur, and if the temperature reduction rate exceeds 20 ° C / hour, the layered compound prepared is polycrystalline Can be.
  • the layered compound prepared in step (1) includes a salt including a salt capable of selectively removing Ca ions contained in the layered compound and a solvent capable of dissolving the salt. Treated with solution to produce layered Ge.
  • the salt may include an anion having a high electronegativity and a cation having an electronegativity value between the alkaline earth metal ion and the Ge ion in order to easily react with the alkaline earth metal ion (Ca ion) included in the layered compound.
  • the salt may be represented by the following Chemical Formula 1, wherein the salt is a cation having an electronegativity value between the alkaline earth metal ions and Ge ions, and M and Cl ions having high electronegativity. It consists of.
  • M may be any one selected from Sn, Al, and Ga
  • X may be any one selected from Cl, F, and I.
  • the solvent may include at least one selected from ethanol, water, acetone and isopropanol, and the composition of the solvent may vary according to the temperature at which step (2) is performed.
  • the salt may be used in an amount sufficient to remove alkaline earth metal ions of the layered compound, but preferably, the layered compound and the salt in the mixed solution may be included in a molar ratio of 1: 1 to 1: 3. If the molar ratio of the layered compound and the salt is less than 1: 1, the alkaline earth metal ions of the layered compound may not be removed to the desired level, and if the molar ratio exceeds 1: 3, the salt There may be a problem such that the precipitate is not dissolved in the mixed solution.
  • the crystal structure of the layered Ge may be changed depending on the temperature at which step (2) is performed.
  • the layered Ge may have a trigonal crystal structure having a space group of Rm-3m, and the step (2) may be 15 to 60 ° C.
  • the layered Ge prepared when carried out at ° C. may have an amorphous crystal structure.
  • step (2) In the preparation of layered Ge having a trigonal crystal structure, if step (2) is performed at less than -40 ° C, the crystallinity of the layered Ge to be produced becomes high, but the reaction time for removing alkaline earth metal ions is excessive. It may increase, and if the crystallinity of the layered Ge produced is not expressed at the desired level when the temperature exceeds 0 ° C., or the layered Ge produced may have an amorphous crystal structure.
  • step (2) In preparing a layered Ge having an amorphous crystal structure, if step (2) is performed at less than 15 ° C., the crystallinity of the layered Ge to be produced may be high and the reaction time for removing alkaline earth metal ions may be increased. When the reaction time exceeds 60 ° C, the reaction time for removing the alkaline earth metal ions may decrease, but the layered structure of the layered Ge may be disrupted.
  • the step (2) may be performed a plurality of times depending on the composition of the mixed solution and the removal rate of Ca ions, but is preferably performed once to maintain the layered structure of the layered Ge.
  • step (2) there may be a reactant formed by reacting alkaline earth metal ions with a salt in addition to the layered Ge.
  • a reactant formed by reacting alkaline earth metal ions with a salt in addition to the layered Ge.
  • the powder obtained through step (2) may be washed with a solvent. Can be.
  • the solvent for removing the reactant may be at least one selected from water, deionized water, methanol and ethanol.
  • the layered Ge according to the present invention has a trigonal crystal structure having an amorphous or space group of Rm-3m, which is different from the existing 3D bulk Ge, and has excellent peelability and has a form of nanosheets. It is easy to peel off, and has a large surface area and excellent ion capacity.
  • the space group has a trigonal crystal structure of Rm-3m.
  • Phase Ge is 2 ⁇ of 15.5 ⁇ 0.2, 26.4 ⁇ 0.2, 35.6 ⁇ 0.2, 45.7 ⁇ 0.2, 48.5 ⁇ 0.2 and 53.6 ⁇ 0.2 in the X-ray diffractogram obtained by powder X-ray diffraction using Cu-K ⁇ rays. It may have a peak at the value and may not have a peak at 2 ⁇ values of 27.4 ⁇ 0.2, 45.6 ⁇ 0.2, 54.0 ⁇ 0.2 and 66.4 ⁇ 0.2.
  • the Ge nanosheets according to the present invention can be obtained by peeling from the layered Ge according to the present invention and have an amorphous or triangular symmetric crystal structure.
  • the Ge nanosheets may have a thickness of 100 nm or less, and if the thickness exceeds 100 nm, the surface area of the Ge nanosheets is lowered to decrease ion storage capacity or the Ge nanosheets. May be difficult to stack.
  • a method of peeling a layered material known in the art may be used, and for example, a method of peeling with energy by ultrasonic waves, a peeling method by invasion of a solvent, a peeling method using a tape, and adhesion Any of the stripping methods using a substance having a surface may be used.
  • step (1) the mixture including Ca powder and Ge powder is heat-treated and then quenched so that the layered CaGe 2 and space group having a trigonal crystal structure having a space group of Rm-3m are formed.
  • a compound containing Ge having a cubic crystal structure of Fd-3m is prepared.
  • the heat treatment may be performed for 6 to 24 hours at 830 ⁇ 1,000 °C, quenching the heat-treated mixture to the layer type CaGe 2 having a trigonal crystal structure (space group) of Rm-3m and space A compound having a lamella structure including Ge having a cubic crystal structure in which the group is Fd-3m can be prepared.
  • Such a lamellar compound is formed only when the molten mixture is quenched, and Ge nanosheets may be prepared from the lamellar compound in step (2) described later.
  • the quenching may be performed at 10 ⁇ 40 °C.
  • the lamellar structure may be formed by alternately stacking a first layer including the layered CaGe 2 and a second layer including the Ge, and the layered type in step (2) described later.
  • the first layer is formed of Ge nanosheets having an amorphous or triangular symmetric crystal structure
  • the second layer has a cubic crystal structure having a space group of Fd-3m. It can be formed of a Ge nanosheet having.
  • step (2) is performed by treating the layered compound with a mixed solution containing a salt capable of selectively removing Ca ions contained in the layered CaGe 2 and a solvent capable of dissolving the salt.
  • a mixed solution containing a salt capable of selectively removing Ca ions contained in the layered CaGe 2 and a solvent capable of dissolving the salt are prepared.
  • composition of the mixed solution for removing Ca ions, the temperature conditions of step (2) and the crystal structure of the Ge nanosheets prepared from the layered CaGe 2 are the same as described above in the manufacturing method of the layered Ge. Detailed description thereof will be omitted.
  • the Ge nanosheets of the trigonal crystal structure and the Ge nanosheets of the monoclinic crystal structure may be peeled off without a separate peeling process.
  • Ge nanosheets prepared by the method of manufacturing Ge nanosheets of the present invention include Ge nanosheets having an amorphous or triangular symmetric crystal structure and Ge nanosheets having a cubic crystal structure having a space group of Fd-3m. .
  • the layered Ge and Ge nanosheets according to the present invention have a wide surface area and excellent ion capacity, when used as an electrode for a lithium ion battery, a lithium ion battery having a reduced capacity loss can be realized.
  • the lithium ion battery may include an electrode, a counter electrode, an separator provided between the electrode and the counter electrode, and an electrolyte solution.
  • the electrode includes the layered Ge or Ge nanosheets according to the present invention, it is possible to minimize the capacity loss due to the volume expansion of the electrode generated during charging and discharging, thereby improving the life of the lithium ion battery.
  • the counter electrode, the separator, and the electrolyte included in the lithium ion battery may adopt a known structure in the field of lithium ion batteries, and thus, the present invention will not be described in detail.
  • layered CaGe 2 For the synthesis of layered CaGe 2 , Ca powder and Ge powder were mixed and then heat-treated at 800 ° C. for 7 days and cooled to give a layered trigonal crystal structure with a space group of Rm-3m. CaGe 2 was obtained.
  • Example 1 The layered Ge prepared in Example 1 was peeled off with Scotch tape (3M) to prepare Ge nanosheets.
  • the Lamellar structure prepared in Preparation Example 2 was mixed with ethanol and SnCl 2 at ⁇ 20 ° C. to remove Ca ions, thereby preparing Ge nanosheets.
  • a commercial 3D bulk Ge (Sigma Aldrich, product no .: 203351) was prepared.
  • the layered Ge (0.08 g) prepared in Example 1 was mixed with Super P (0.01 g) and PVDF (0.01 g). Thereafter, the mixture was mixed with an NMP solvent to prepare a slurry for the electrode, which was coated on the copper thin film by a doctor blade method to 2 ⁇ m, and then heat treated to produce a Ge electrode.
  • the Ge electrode was laminated with a lithium metal electrode, a separator was inserted between the two electrodes, and an electrolyte solution containing LiPF 6 (1.0 M) dissolved in an organic solvent in which EC and DEC were mixed at a volume ratio of 1: 1 was injected.
  • a coin-type half cell was assembled to fabricate a lithium ion battery.
  • the crystal structure of the layered CaGe 2 (preparation example 1) is a trigonal having a space group of Rm-3m, and the layered types of Examples 1 and 2 It can be seen that Ge has a crystal structure different from the bulk Ge of the existing 3D crystal structure.
  • the layered Ge of Example 1 has a higher crystallinity than the layered Ge of Example 2.
  • the layered Ge (Example 1) has a stronger Ge-Ge in-plane strain than 3D Ge (Comparative Example 1), which is a buckled angle of Ge. Means increased.
  • Ge prepared from layered CaGe 2 is layered. It can be seen that it has a significantly different structure compared to the 3D bulk Ge shown in FIG. 5A.
  • 5D shows an SEM image of the layer structure of Example 1 with different magnifications, and the layer structure of the layered Ge according to Example 1 can be clearly confirmed.
  • the crystal structures of 3D bulk Ge and layered CaGe 2 are different.
  • the layered Ge (Example 1) having Ca ions removed at ⁇ 20 ° C. has higher crystallinity and has a trigonal crystal structure than the layered Ge having removed Ca ions at room temperature (Example 2). You can check it.
  • the layered Ge shows that the Ca element content is significantly reduced.
  • AFM analysis was performed on the Ge nanosheets according to Example 3, and the results are shown in FIG. 8. Referring to FIG. 8, it can be seen that the thickness of the Ge nanosheets is 9 nm and 29 nm.
  • FIG. 9A is a graph showing charge and discharge curves of a lithium ion battery (manufacture example 1) including a layered Ge. Referring to FIG. 9A, it can be seen that the lithium ion battery of Preparation Example 1 has stable charge and discharge characteristics. .
  • Figure 9b is a discharge capacity graph according to the cycle, the lithium ion battery according to Preparation Example 1 shows that the first cycle efficiency of about 80% performance, but from the second cycle it can be seen that the cycle efficiency increased to about 96%.
  • the discharge capacity in the first cycle was the same as that of Preparation Example 1.
  • Comparative Preparation Example 1 had a capacity of about 1,396 mAh / g, but after 50 cycles Preparation Example 1 shows a capacity of about 163 mAh / g while Comparative Production Example 1 has a capacity of about 46 mAh Had Through this, it can be seen that when using the layered Ge electrode according to the present invention, capacity loss due to volume expansion of the electrode can be minimized.

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Abstract

La présente invention concerne du Ge en couches, son procédé de fabrication, et une nanofeuille de Ge libérée à partir de celui-ci et, plus spécifiquement, un Ge en couches, qui a une structure cristalline bidimensionnelle contrairement à un Ge volumineux classique, est facile à libérer sous la forme d'une nanofeuille en raison de son excellente aptitude au décollement, et a une grande surface et une excellente capacité ionique, un procédé de fabrication de celui-ci, une nanofeuille de Ge libérée à partir de celui-ci, et une électrode la comprenant pour une batterie au lithium-ion.
PCT/KR2019/008903 2018-05-18 2019-07-18 Ge en couches, son procédé de fabrication, nanofeuille de ge pelée à partir de celui-ci, et électrode la comprenant pour batterie au lithium-ion WO2019221584A2 (fr)

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KR10-2018-0057451 2018-05-18
KR1020180057451A KR102080829B1 (ko) 2018-05-18 2018-05-18 층상형 Ge, 이의 제조 방법, 이로부터 박리된 Ge 나노시트 및 이를 포함하는 리튬이온전지용 전극

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WO2019221584A3 WO2019221584A3 (fr) 2020-01-09
WO2019221584A9 WO2019221584A9 (fr) 2020-02-27

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