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WO2014126413A1 - Matériau actif d'anode pour accumulateur au sodium, procédé de fabrication d'électrode l'utilisant et accumulateur au sodium le comprenant - Google Patents

Matériau actif d'anode pour accumulateur au sodium, procédé de fabrication d'électrode l'utilisant et accumulateur au sodium le comprenant Download PDF

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WO2014126413A1
WO2014126413A1 PCT/KR2014/001220 KR2014001220W WO2014126413A1 WO 2014126413 A1 WO2014126413 A1 WO 2014126413A1 KR 2014001220 W KR2014001220 W KR 2014001220W WO 2014126413 A1 WO2014126413 A1 WO 2014126413A1
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secondary battery
phosphorus
active material
sodium
sodium secondary
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Korean (ko)
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오승모
김영진
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SNU R&DB Foundation
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SNU R&DB Foundation
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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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • 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
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a cathode active material for a sodium secondary battery, a method for manufacturing an electrode using the same, and a sodium secondary battery including the same. More particularly, by forming a cathode active material using a phosphorus-carbon composite, a reversible capacity for sodium ions is achieved. It relates to a large, excellent initial efficiency of the anode active material for sodium secondary battery, a method for producing an electrode using the same and a sodium secondary battery comprising the same.
  • a secondary battery is a battery that can be used repeatedly through a charging process that is reverse to the discharge where chemical energy is converted into electrical energy.
  • lithium secondary batteries can be used in various portable electronic devices such as laptops and mobile phones, and the market is expected to expand greatly in the future for electric vehicles and energy storage.
  • lithium reserves are limited and thus secondary batteries are required.
  • Japanese Patent Application Laid-Open No. 2007-35588 applies carbon as a negative electrode active material of a sodium ion secondary battery, but has the ability to reversibly store and discharge sodium ions, that is, a reversible capacity of less than 300 mAh / g. There is. Therefore, in order to implement a sodium secondary battery, it is urgent to develop a negative electrode and a positive electrode material having a high reversible capacity of sodium ions and a low charge / discharge voltage.
  • an object of the present invention is to solve such a conventional problem, and can reversibly store and discharge sodium ions, thereby improving electrical conductivity by compounding carbon in red phosphorus having excellent storage and releasing ability of sodium, and improving sodium conductivity.
  • the purpose of the present invention is to provide a negative electrode active material, an electrode using the same, and a sodium secondary battery including the same, including a phosphorus-carbon composite having high capacity and high efficiency by increasing reactivity.
  • cathode active material comprising a phosphorus-carbon composite having a reversible capacity of 650 mAh / g or more and having a low charge / discharge voltage, an electrode using the same, and a sodium secondary battery including the same, compared to a cathode active material using only carbon or red phosphorus.
  • the negative electrode active material for a sodium secondary battery including a phosphorus-carbon composite
  • phosphorus in the phosphorus-carbon composite is at least one of red phosphorus, black phosphorus, white phosphorus or sulfur Can be.
  • the weight ratio of the phosphorus and carbon of the phosphorus-carbon composite may be 1: 0.1 to 1: 2.5.
  • the average particle diameter of the phosphorus-carbon composite may be 0.01 to 10 ⁇ m, and the primary particle size may be 5 to 500 nm.
  • the phosphorus-carbon composite may further include graphene.
  • Carbon of the phosphorus-carbon composite may have a specific surface area of 10 to 3000 m 2 / g.
  • Carbon of the phosphorus-carbon composite may include graphite.
  • Phosphorus of the phosphorus-carbon complex may be red phosphorus, and the red phosphorus may be in an amorphous phase.
  • the amorphous phase has a signal-to-noise ratio of less than 50 compared to the noise appearing at the baseline when X-ray diffraction analysis is performed at a scan rate of 1 o / min to 16 o / min per minute and 20 o to 70 o at 0.01 o intervals. Can be.
  • the negative electrode active material may have a peak at a wavenumber of 1582 cm ⁇ 1 in Raman spectroscopy.
  • the cathode material may have a peak appearing at a wavenumber of 1582 cm ⁇ 1 as measured by Raman spectroscopy than a peak appearing at a wave number of 1332 cm ⁇ 1 .
  • the negative electrode active material may operate in a voltage range of 0.2 to 1.0V in preparation for the reduction potential of sodium.
  • the negative electrode active material may have a reversible capacity of 650 mAh / g or more.
  • a paste preparation step of preparing a paste by mixing a negative active material powder, a binder and a dispersion consisting of a phosphorus-carbon composite An application step of applying the paste to an electrode current collector; And a drying step of drying the paste at a temperature of 50 to 200 ° C.
  • the dispersion may be 10 to 200 parts by weight, and the binder may be 3 to 50 parts by weight based on 100 parts by weight of the negative electrode active material.
  • the dispersion may include at least one of N-methylpyrrolidone, isopropyl alcohol, acetone or water.
  • the binder is polytetrafluoroethylene, polyvinylidene fluoride, cellulose styrene-butadiene rubber, polyimide, polyacrylic acid, polyacrylic acid alkali salt, polymethyl methacrylate or polyacrylonitrile It may include at least one of the reels.
  • the paste may further include a powdery conductive material, and the conductive material may include at least one of carbon black, vapor-grown carbon fiber, or graphite.
  • the conductive material may be 1 to 30 parts by weight based on 100 parts by weight of the negative electrode active material.
  • a sodium secondary battery according to an embodiment of the present invention is a positive electrode including at least one of a negative electrode, a sodium metal oxide, sodium metal phosphate, sodium metal fluoride oxide or sodium metal fluoride oxide containing the negative electrode active material, the It may comprise a separator and an electrolyte present between the negative electrode and the positive electrode.
  • the sodium metal oxide is Na x CoO 2 , Na x Co 2/3 Mn 1/3 O 2 , Na x Fe 1/2 Mn 1/2 O 2 , NaCrO 2 , NaLi 0.2 Ni 0.25 Mn 0.75 O 2.35 , Na 0.44 MnO 2 , NaMnO 2 , Na 0.7 VO 2 , Na 0.33 V 2 O 5 , wherein 0 ⁇ x ⁇ 1.
  • the sodium metal phosphate may include at least one of Na 3 V 2 (PO 4 ) 3 , NaFePO 4 , NaMn 0.5 Fe 0.5 PO 4 , Na 3 V 2 (PO 4 ) 3 .
  • the sodium metal fluorophosphate may include at least one of Na 2 FePO 4 F, Na 3 V 2 (PO 4 ) 3 .
  • the sodium metal fluoride oxide may be NaFeSO 4 F.
  • the electrolyte may be dissolved in a sodium salt comprising at least one of NaClO 4 , NaAsF 6 , NaBF 4 , NaPF 6 , NaSbF 6 , NaCF 3 SO 3 or NaN (SO 2 CF 3 ) 2 in an organic solvent.
  • the organic solvent is ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, isopropyl methyl carbonate, vinylene carbonate, ethylene fluoride carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, at least one of ⁇ -butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxene, 4-methyl-1,3-dioxene, diethyl ether, tetraethylene glycol dimethyl ether or sulfolane It may include one.
  • the sodium salt may be 0.1 to 2 molar concentrations.
  • the electrolyte may include 0.1 to 10% by weight of ethylene fluoride as an additive.
  • the initial efficiency is high, and the output characteristics are excellent.
  • the formation of the phosphorus-carbon composite can be formed by a simple method of mechanically synthesizing phosphorus and carbon using ball milling at room temperature, so that the anode active material can be easily produced economically.
  • FIG. 1 is a flowchart sequentially illustrating a method of manufacturing an electrode for sodium secondary battery according to the present invention.
  • FIG. 2A is a graph showing the results of X-ray diffraction analysis of Example 1 negative active material in Experiment 1.
  • Figure 2b is a photograph taken in Example 1, the negative electrode active material of Example 1 with a transmission electron microscope.
  • FIG. 3A is a graph showing the results of X-ray diffraction analysis of Example 2 negative active material in Experiment 1.
  • Figure 3b is a photograph taken in Example 1, the negative electrode active material of Example 2 with a transmission electron microscope.
  • FIG. 4A is a graph showing the results of X-ray diffraction analysis of Comparative Example 1 negative electrode active material in Experiment 1.
  • FIG. 4A is a graph showing the results of X-ray diffraction analysis of Comparative Example 1 negative electrode active material in Experiment 1.
  • Figure 4b is a photograph taken with a scanning electron microscope in Comparative Example 1, the negative electrode active material of Comparative Example 1.
  • FIG. 5 is a graph showing charge and discharge curves showing electrochemical characteristics associated with sodium ion storage of Example 3 in Experiment 2.
  • FIG. 5 is a graph showing charge and discharge curves showing electrochemical characteristics associated with sodium ion storage of Example 3 in Experiment 2.
  • FIG. 6 is a graph showing charge and discharge curves showing electrochemical characteristics associated with sodium ion storage of Example 4 in Experiment 2.
  • FIG. 6 is a graph showing charge and discharge curves showing electrochemical characteristics associated with sodium ion storage of Example 4 in Experiment 2.
  • FIG. 7 is a graph showing charge and discharge curves showing electrochemical characteristics associated with sodium ion storage of Example 7 in Experiment 2.
  • FIG. 8 is a graph showing charge and recharge curves showing electrochemical properties associated with sodium ion storage of Example 8 in Experiment 2.
  • FIG. 9 is a graph showing charge and discharge curves showing electrochemical characteristics related to sodium ion storage of Comparative Example 2 in Experiment 2.
  • Example 11 is a graph showing the results of ex-situ X-ray diffraction analysis according to the charge and discharge of Example 3 in Experiment 4.
  • FIG. 12 is a graph showing charge and discharge curves according to current magnitudes of Example 3 in Experiment 5.
  • FIG. 12 is a graph showing charge and discharge curves according to current magnitudes of Example 3 in Experiment 5.
  • FIG. 13 is a graph showing discharge capacity according to current magnitudes of Examples 3 to 6 in Experiment 5.
  • Example 14 is a photograph taken by a scanning electron microscope of Example 9 the negative electrode active material in Experiment 1.
  • FIG. 15 is a result of photographing the cross-section of the cathode active material of Example 9 with a scanning electron microscope and analyzing the components with an energy dispersive X-ray spectrometer (EDS).
  • EDS energy dispersive X-ray spectrometer
  • Example 16 is a graph showing the results of X-ray diffraction analysis of Example 9, Comparative Example 1 and Comparative Example 5 negative electrode active material in Experiment 1.
  • FIG. 17 is a graph showing Raman spectroscopy results of Example 9 and Comparative Example 1 negative electrode active material in Experiment 1.
  • FIG. 17 is a graph showing Raman spectroscopy results of Example 9 and Comparative Example 1 negative electrode active material in Experiment 1.
  • FIG. 18 is a graph showing charge and discharge curves showing electrochemical characteristics associated with sodium ion storage of Example 10 in Experiment 2.
  • Example 21 is a graph showing the cycle characteristics when the sodium secondary battery of Example 11 is applied in Experiment 3.
  • FIG. 22 is a graph showing charge and discharge curves showing electrochemical characteristics associated with storage of sodium ions of Example 12 in Experiment 2.
  • FIG. 23 is a graph showing the cycle characteristics when the sodium secondary battery of Example 12 is applied in Experiment 3.
  • FIG. 23 is a graph showing the cycle characteristics when the sodium secondary battery of Example 12 is applied in Experiment 3.
  • FIG. 25 is a graph showing the cycle characteristics when the sodium secondary battery of Example 13 is applied in Experiment 3.
  • FIG. 25 is a graph showing the cycle characteristics when the sodium secondary battery of Example 13 is applied in Experiment 3.
  • FIG. 26 is a graph showing discharge capacity according to current magnitudes related to sodium ion storage of Example 10 in Experiment 6.
  • FIG. 26 is a graph showing discharge capacity according to current magnitudes related to sodium ion storage of Example 10 in Experiment 6.
  • FIG. 27 is a graph showing discharge capacity according to current magnitudes related to sodium ion storage of Example 11 in Experiment 6.
  • the negative electrode active material for sodium secondary battery of the present invention comprises a phosphorus-carbon composite.
  • Phosphorus has the ability to reversibly store / discharge sodium ions, but it is very low in electrical conductivity and cannot be used as an electrode material.
  • the present invention solves the low electrical conductivity problem of phosphorus by complexing with carbon having high electrical conductivity.
  • Phosphorus has various allotropes, and red phosphorus, black phosphorus, white phosphorus, or sulfur phosphorus may be used as a composite material with carbon in the present invention, but red phosphorus is most effective.
  • red phosphorus has a great advantage in the diffusion rate of ions because it has an amorphous phase without crystallinity, compared with black phosphorus, white phosphorus, and yellow phosphorus, and is more advantageous for ion diffusion because it forms a dense structure with low density. .
  • the weight ratio of phosphorus to carbon of the phosphorus-carbon composite is preferably 1: 0.1 to 1: 2.5, more preferably 1: 0.4 to 1: 1. If the weight ratio of phosphorus and carbon is less than 1: 0.1, there is a problem of low electrical conductivity, and if it exceeds 1: 2.5, the reversible capacity is small and is not suitable as an active material.
  • the phosphor-carbon composite preferably has an average particle diameter of 0.01 to 10 ⁇ m, more preferably 0.1 to 3 ⁇ m. If the average particle diameter is less than 0.01 ⁇ m, the reactivity with sodium decreases, making the electrode difficult. If the average particle diameter exceeds 10 ⁇ m, the diffusion of sodium ions becomes difficult and the possibility of defects caused by the large particles in the electrode manufacturing increases. .
  • the primary particle diameter of the phosphorus-carbon composite is preferably 5 to 500 nm, more preferably 10 to 100 nm.
  • the primary particle size is less than 10 nm or more than 100 nm, not only the reactivity with sodium is rather reduced, but also there is a problem that electrode formation is difficult.
  • the primary particle diameter refers to the diameter of the primary particles
  • the primary particles are particles constituting the powder and aggregate, particles of the smallest unit that does not break the bond between molecules, each particle is a different particle It means the particles in a state of being present alone without aggregation with.
  • the secondary particle means a particle formed by aggregation of a plurality of primary particles, that is, aggregated particles.
  • the unit representing the unbroken mass is called primary particles, and the case where these primary particles aggregate to form powder is called secondary particles.
  • the phosphorus-carbon composite of the preferred embodiment of the present invention may further include graphene.
  • Graphene has excellent electrical conductivity, a large surface area of more than 2600 m 2 / g, and is chemically stable.
  • the space between the graphene can buffer the volume expansion and contraction of the electrode generated during the charging / discharging process, it can improve the cycle efficiency of the battery when implementing the negative electrode active material further comprising graphene .
  • the content of graphene is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the phosphorus-carbon composite.
  • the carbon of the phosphorus-carbon composite preferably has a specific surface area of 10 to 3000 m 2 / g, more preferably 10 to 100 m 2 / g.
  • the phosphorus of the phosphorus-carbon complex is most preferably red phosphorus, which is characterized in that the amorphous phase.
  • the amorphous phase means that the characteristic peak does not appear when the X-ray diffraction analysis is measured at 0.01 o intervals from 20 o to 70 o at a scanning speed of 1 o / min to 16 o / min per minute.
  • the red phosphorus-carbon composite of the present invention is advantageous as the crystallinity is lower, the degree of crystallization can be determined by the experimental results of X-ray diffraction analysis (XRD). Therefore, the results of several experiments confirmed that the effect of the present invention can be exerted when the characteristic peak does not appear by performing X-ray diffraction analysis under the above conditions.
  • the presence of the characteristic peak can be determined by whether a signal having a characteristic peak sufficiently larger than the noise appearing in the base line is generated. When a sufficiently large signal was generated for the noise and the signal-to-noise ratio (S / N ratio) was 50 or more, it was determined that a characteristic peak existed.
  • the magnitude of the noise refers to the amplitude of the base line in the region where no characteristic peak occurs, and it is also possible to set the standard deviation as a reference.
  • the signal-to-noise ratio is a value representing the magnitude ratio of the generated signal relative to the amount of noise based on the amplitude of the signal appearing on the baseline. More preferably, the signal having the signal-to-noise ratio of 10 or more does not occur. Is most effective. As a result of several experiments, the above conditions are most preferable to satisfy the effects of the present invention.
  • the type of carbon in the phosphorus-carbon composite anode active material is not limited, it is preferable that the electrical conductivity is high when constructing the composite.
  • a material including carbon black or graphite may be used, and in particular, it is preferable to have a structure having regularity manufactured using graphite.
  • the regularity is the presence of a peak showing the regularity in Raman spectroscopy, it is advantageous that the G-band around 1582cm -1 due to carbon developed in the phosphor-carbon composite anode active material, in particular 1332cm -1 A structure in which the G band is more developed than the peak of the adjacent D band is preferable.
  • Phosphorus-carbon composite anode active material maximizes the increase in reactivity, and realizes high capacity, excellent output characteristics, and charging characteristics.
  • the phosphorus-carbon composite anode active material according to the present invention operates in a voltage range of 0.2 to 1.0 V in comparison with the reduction potential of sodium, so that the charge and discharge voltage is very low.
  • the reversible capacity per weight exerts an effect of 650mAh / g or more, it can be realized a reversible capacity of 1300mAh / g or more as shown in the following experiment.
  • the phosphorus-carbon composite anode active material of the present invention is most preferably implemented as a cathode active material of sodium secondary battery, but this does not limit the application to other batteries.
  • the method of manufacturing an electrode using the phosphorus-carbon composite anode active material according to the present invention comprises a paste preparation step (S10), coating step (S20) and drying step (S30). .
  • Paste preparation step (S10) is a step of preparing a paste by mixing a binder and a dispersion in a negative electrode active material powder consisting of a phosphorus-carbon composite.
  • the negative electrode active material composed of the phosphorus-carbon composite is as described above.
  • the binder is used in the form of a powder to make easily into a paste. Mixing is preferably performed through a stirring process, but any method may be used as long as it can be mixed evenly.
  • Phosphorus-carbon composites synthesize phosphorus and carbon using mechanical milling.
  • Mechanical milling method is loaded with phosphorus and carbon together with a ball and mounted in a high-energy ball mill to perform mechanical synthesis at a rotation speed of 200 to 500 or more times per minute, which is performed in an argon gas atmosphere to minimize the effects of oxygen or moisture. It is preferable.
  • This milling can be performed at room temperature, so that the phosphor-carbon composite can be easily synthesized in a simple process without a separate process.
  • graphene may be further included to form a complex.
  • the binder comprises at least one of polytetrafluoroethylene, polyvinylidene fluoride, cellulose styrenebutadiene rubber, polyimide, polyacrylic acid, alkali alkali salt, polymethyl methacrylate or polyacrylonitrile can do.
  • the amount of the binder is effective to include 3 to 50 parts by weight based on 100 parts by weight of the negative electrode active material. If the binder is less than 3 parts by weight, the binder may not fully serve, and if it exceeds 50 parts by weight, there is a problem of inhibiting the reactivity of the negative electrode active material.
  • the dispersion may include at least one of N-methylpyrrolidone, isopropyl alcohol, acetone or water. This serves to easily disperse the negative electrode active material and the binder.
  • the content of the dispersion is preferably 10 to 200 parts by weight, more preferably 50 to 100 parts by weight based on 100 parts by weight of the negative electrode active material. If the dispersion is less than 10 parts by weight, there is a problem that the mixing action is difficult because the dispersion action does not occur sufficiently, if it exceeds 200 parts by weight, there is a problem that the economic efficiency, such as too thin to take a long drying process.
  • a conductive material may be further added.
  • the conductive material is mixed with the negative electrode active material, the binder, and the dispersion, and further reduces the resistance of the electrode, thereby increasing the output of the battery.
  • the conductive material is at least one of carbon black, vapor grown carbon fiber, or graphite, and may be powdery. It is preferable to add 1-30 weight part with respect to 100 weight part of negative electrode active materials, More preferably, it is effective to add 10-20 weight part. If the conductive material is less than 1 part by weight, the effect of reducing the resistance of the electrode is insignificant, and if it exceeds 30 parts by weight, not only economic efficiency is reduced, but rather there is a problem that can reduce the effect of the negative electrode active material.
  • the applying step (S20) is a step of applying the paste to the electrode current collector.
  • the current collector for the electrode is a highly conductive metal, and should be easily adhered to the paste. If the metal having such a performance is not limited in use, but at least one of copper, aluminum, stainless steel, nickel can be implemented to excellent performance.
  • the method of uniformly applying the paste prepared by the paste preparation step (S10) to the electrode current collector is possible in various ways, but after dispensing the paste on the electrode current collector, a doctor blade or the like is used. It is most preferable to uniformly disperse the liquid, and in some cases, a method of distributing and dispersing in one process may be used. In addition, methods such as die casting, comma coating, and screen printing may be used, and may be formed on a separate substrate and then bonded to the current collector by pressing or lamination. Can also be.
  • the drying step (S30) is a step of drying the paste.
  • the drying temperature is preferably 50 to 200 ° C, more preferably 100 to 150 ° C. If the temperature is less than 50 ° C., there is a problem in that the drying time is increased and the economy is inferior. If the temperature is more than 200 ° C., the paste is carbonized or rapidly dried to increase the resistance of the electrode. Drying step (S30) is a process of evaporating the dispersion medium or the solvent passing through the hot air blowing region may be made at atmospheric pressure.
  • the electrode manufactured by the method of manufacturing an electrode using the phosphorus-carbon composite anode active material of the present invention may be used for a sodium secondary battery, but is not limited thereto.
  • the sodium secondary battery including the phosphorus-carbon composite anode active material according to the present invention comprises a negative electrode, a positive electrode, a separator and an electrolyte.
  • the negative electrode includes the phosphorous-carbon composite negative active material described above.
  • the anode may include at least one of sodium metal oxide, sodium metal phosphate, sodium metal phosphate or sodium metal sulphate.
  • the sodium metal oxide is Na x CoO 2 , Na x Co 2/3 Mn 1/3 O 2 , Na x Fe 1/2 Mn 1/2 O 2 , NaCrO 2 , NaLi 0.2 Ni 0.25 Mn 0.75 O 2.35 , Na 0.44 At least one of MnO 2 , NaMnO 2 , Na 0.7 VO 2 , Na 0.33 V 2 O 5 , wherein 0 ⁇ x ⁇ 1 , and the sodium metal phosphate is Na 3 V 2 (PO 4 ) 3 , NaFePO 4 , NaMn 0.5 Fe 0.5 PO 4 , Na 3 V 2 (PO 4 ) 3 It may include at least one, the sodium metal fluoride is Na 2 FePO 4 F, Na 3 V 2 (PO 4 It may include at least one of 3 ), the sodium metal fluoride oxide may be NaFeSO 4 F.
  • the separator is present between the cathode and the anode. This serves to block internal short circuits of the two electrodes and to impregnate the electrolyte.
  • the material of the separator is preferably made of at least one of polypropylene and polyethylene to maximize the performance of the battery using the negative electrode and the positive electrode.
  • the electrolyte is a sodium salt dissolved in an organic solvent, including at least one of NaClO 4 , NaAsF 6 , NaBF 4 , NaPF 6 , NaSbF 6 , NaCF 3 SO 3 or NaN (SO 2 CF 3 ) 2 in an organic solvent Can be done.
  • the organic solvent is ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, isopropyl methyl carbonate, vinylene carbonate, ethylene fluoride carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, ⁇ -butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxene, 4-methyl-1,3-dioxene, diethyl ether, tetraethylene glycol dimethyl ether or sulfolane And tetraethylene glycol dimethyl is effective. In some cases, two or more may be used in combination. It is effective to use the electrolyte to maximize the performance of the sodium secondary battery using the negative electrode and the positive electrode.
  • the phosphorus-carbon composite anode active material according to the present invention a method of manufacturing an electrode using the same, and an embodiment of a sodium secondary battery including the same, will demonstrate the effect of the present invention.
  • the mixture prepared by mixing red phosphorus and carbon in a weight ratio of 7: 3 was immersed with a ball in a cylindrical vial and milled for 20 hours after mounting on a high energy ball mill. Carbon black was used.
  • the weight ratio of the ball and the mixture was maintained in a ratio of 10 to 30 to 1, and was carried out in a glove box of argon gas atmosphere to prepare a phosphorus-carbon composite anode active material.
  • a phosphorus-carbon composite anode active material was prepared in the same manner as in Example 1 except that the mixture was prepared by mixing red phosphorus and carbon in a weight ratio of 5: 5.
  • a phosphorus-carbon composite anode active material was prepared in the same manner as in Example 1 except that carbon was used as graphite.
  • Red phosphorus (Aldrich) was used as the negative electrode active material instead of the mixture.
  • Red phosphorus and graphite were prepared in a mixture only without a ball milling process at a mass ratio of 1: 1.
  • the cathode active material according to Example 9 was processed by using a focused ion beam (FIB), and the elements were analyzed using a scanning electron microscope and an energy dispersive X-ray spectrometer.
  • FIB focused ion beam
  • X-ray diffraction analysis results and the particle shape observed by transmission electron microscope of Example 1 are shown in Figs. 2a and 2b, respectively.
  • Phosphorus and carbon of the phosphorus-carbon composite anode active material of Example 1 both appeared to be in an amorphous phase, and it can be seen that the average particle diameter is 0.1 to 3 ⁇ m in size.
  • Example 2 X-ray diffraction analysis results and the particle shape observed with a scanning electron microscope of Example 2 are shown in Figs. 3a and 3b, respectively. As in Example 1, Example 2 also appeared in both the phosphorus and carbon of the phosphorus-carbon composite anode active material in an amorphous phase, it can be seen that the average particle size is 0.1 to 3 ⁇ m size.
  • Comparative Example 1 X-ray diffraction analysis of Comparative Example 1 and the particle shape observed by transmission electron microscope are shown in Figs. 4a and 4b, respectively.
  • Comparative Example 1 was also amorphous, but the average particle diameter was widely distributed in the range of 0.01 to 10 ⁇ m. That is, in the case of red phosphorus, red phosphorus itself is not suitable as an active material due to its low electrical conductivity, and the average particle diameter may be wide so that diffusion of sodium ions may be difficult, making it difficult to use as a negative electrode active material.
  • Example 9 X-ray diffraction analysis results of Example 9 and the particle shape observed by scanning electron microscopy prepared by scanning electron microscope and focused ion beam are shown in Figure 14 and 15, respectively.
  • Example 9 X-ray diffraction analysis results for Example 9 and Comparative Examples 1 and 5 are shown in FIG. 16.
  • the characteristic peaks shown in Comparative Examples 1 and 5 were synthesized in the disappeared amorphous state.
  • Example 9 and Comparative Example 1 Raman spectroscopic analysis results of Example 9 and Comparative Example 1 are shown in FIG. 17. X-ray diffraction analysis showed that the negative electrode active material of Example 9, which did not show any peak, was regular in a short period. The peak appears at a wavenumber of 1582 cm -1 corresponding to the graphite structure of carbon, which is larger than the peak at 1332 cm -1 at the diamond structure.
  • the electrode was prepared for the sample prepared above.
  • An electrode was prepared using the phosphorus-carbon composite anode active material prepared in Example 1 above.
  • the paste prepared by mixing and stirring a phosphorus-carbon composite anode active material, carbon black as a conductive material, and polyacrylic acid as a binder in a weight ratio of 70:10:20 was stirred on a copper current collector and dried at 120 ° C. to remove moisture.
  • the dried electrode was pressed using a roll press, cut into a required size, and dried in a vacuum oven at 120 ° C. for at least 12 hours to remove residual moisture. Using this electrode, a 2032 size coin cell was fabricated inside an argon glove box.
  • sodium metal foil was used as the counter electrode, and an electrochemical cell was prepared using 0.8 mol of NaClO 4 / ethylene carbonate (EC): diethyl carbonate (DEC) (volume ratio 1: 1) as the electrolyte. It was.
  • An electrode was manufactured in the same manner as in Example 3, except that the electrode was manufactured using the phosphorus-carbon composite anode active material prepared in Example 2, and an electrochemical cell was prepared in the same manner.
  • the mixture prepared by mixing red phosphorus and carbon in a weight ratio of 9: 1 was immersed with a ball in a cylindrical vial and milled for 20 hours after mounting in a high energy ball mill. Carbon black was used.
  • the weight ratio of the ball and the mixture was maintained in a ratio of 10 to 30 to 1, the same method as in Example 3 except that the electrode was prepared using a phosphorous-carbon composite anode active material by performing in a glove box of argon gas atmosphere An electrode was prepared, and an electrochemical cell was prepared in the same manner.
  • the mixture prepared by mixing red phosphorus and carbon in a weight ratio of 8: 2 was immersed with a ball in a cylindrical vial and milled for 20 hours after mounting in a high energy ball mill. Carbon black was used.
  • the weight ratio of the ball and the mixture was maintained in a ratio of 10 to 30 to 1, the same method as in Example 3 except that the electrode was prepared using a phosphorous-carbon composite anode active material by performing in a glove box of argon gas atmosphere An electrode was prepared, and an electrochemical cell was prepared in the same manner.
  • Red phosphorus, carbon, and graphene were mixed in a weight ratio of 70: 30: 5, dispersed in distilled water, and dried in an oven to remove moisture to prepare a mixture.
  • An electrode was manufactured in the same manner as in Example 3, except that the electrode was manufactured using the composite anode active material, and an electrochemical cell was prepared in the same manner.
  • An electrode was prepared in the same manner as in Example 3, except that polyvinylidenedifluoride (PVdF) dissolved in N-methylpyrrolidone was used as a binder, and an electrochemical cell was prepared in the same manner.
  • PVdF polyvinylidenedifluoride
  • An electrode was manufactured in the same manner as in Example 3, except that the electrode was manufactured using the phosphorus-carbon composite anode active material prepared in Example 9, and an electrochemical cell was prepared in the same manner.
  • An electrode was prepared in the same manner as in Example 10, and an electrochemical cell was prepared in the same manner as in Example 10 except that 5 wt% of ethylene carbonate was added to the electrolyte.
  • An electrode was manufactured in the same manner as in Example 10.
  • An electrochemical cell was prepared in the same manner as in Example 10, except that 1.0 mol of NaPF 6 was used instead of 0.8 mol of NaClO 4 for the electrolyte.
  • An electrode was prepared using red phosphorus according to Comparative Example 1 as a negative electrode active material.
  • the negative electrode active material, carbon black as a conductive material, and polyacrylic acid as a binder were mixed at a weight ratio of 70:10:20 and stirred to coat a paste prepared on a copper current collector and dried at 120 ° C. to remove moisture.
  • the dried electrode was pressed using a roll press, cut into a required size, and dried in a vacuum oven at 120 ° C. for at least 12 hours to remove residual moisture. Using this electrode, a 2032 size coin cell was fabricated inside an argon glove box.
  • sodium metal foil was used as the counter electrode, and an electrochemical cell was prepared using 0.8 mol of NaClO 4 / ethylene carbonate (EC): diethyl carbonate (DEC) (volume ratio 1: 1) as the electrolyte. It was.
  • the mixture prepared by mixing red phosphorus and carbon in a weight ratio of 2.5: 7.5 was infiltrated with a ball in a cylindrical vial and milled for 20 hours after mounting on a high energy ball mill. Carbon black was used.
  • the weight ratio of the ball and the mixture was maintained at a ratio of 10 to 30 to 1, it was carried out in a glove box of argon gas atmosphere to prepare a phosphorus-carbon composite anode active material.
  • the paste prepared by mixing and stirring a phosphorus-carbon composite anode active material, carbon black as a conductive material, and polyacrylic acid as a binder in a weight ratio of 70:10:20 was stirred on a copper current collector and dried at 120 ° C. to remove moisture.
  • the dried electrode was pressed using a roll press, cut into a required size, and dried in a vacuum oven at 120 ° C. for at least 12 hours to remove residual moisture.
  • a 2032 size coin cell was fabricated inside an argon glove box.
  • sodium metal foil was used as the counter electrode, and an electrochemical cell was prepared using 0.8 mol of NaClO 4 / ethylene carbonate (EC): diethyl carbonate (DEC) (volume ratio 1: 1) as the electrolyte. It was.
  • An electrode was prepared using carbon as a negative electrode active material.
  • the carbon negative electrode active material, carbon black as a conductive material, and polyacrylic acid as a binder were mixed in a weight ratio of 70:10:20 and stirred to coat a paste prepared on a copper current collector and dried at 120 ° C. to remove moisture.
  • the dried electrode was pressed using a roll press, cut into a required size, and dried in a vacuum oven at 120 ° C. for at least 12 hours to remove residual moisture. Using this electrode, a 2032 size coin cell was fabricated inside an argon glove box.
  • sodium metal foil was used as the counter electrode, and an electrochemical cell was prepared using 0.8 mol of NaClO 4 / ethylene carbonate (EC): diethyl carbonate (DEC) (volume ratio 1: 1) as the electrolyte. It was.
  • Example 3 The constant current charge and discharge curves of Example 3 are shown in FIG. 5.
  • the charge capacity of the first cycle is 1557 mAh / g and the discharge capacity is 1323 mAh / g, which is very large and has an initial efficiency of 85%.
  • the second cycle is charging and discharging with a value similar to the first discharge capacity.
  • the 1890mAh / g has a high reversibility corresponding to 73% of the theoretical capacity of the phosphorus (P).
  • P phosphorus
  • most of the charge and discharge occurs in the range of 0.3 to 0.8V, which is a desirable characteristic as the negative electrode of the sodium secondary battery.
  • the charge-discharge voltage is in the range of 0.3 to 0.8V, so that there is no problem of electrodeposition of sodium and a problem of decreasing the output voltage of the complete cell.
  • Example 4 The constant current charge and discharge curves of Example 4 are shown in FIG. 6. As shown in FIG. 6, the charge capacity of the first cycle is 903 mAh / g, and the discharge capacity is 683 mAh / g, showing a gentle slope curve. In Example 5, the content of red phosphorus was lower than that of Example 4, so the capacity and initial efficiency appeared to be somewhat lower, but the initial efficiency reached 75%, and the charge / discharge voltage was in the range of 0.3 to 0.8V.
  • Example 6 when the battery was charged and discharged at a constant current of 286 mA / g, the discharge capacity was 1117 mAh / g, which is not sufficient for the phosphorus content because the electric conductivity is not high due to the lack of carbon, but the capacity is not high. Shows capacity.
  • Example 5 when the charge and discharge at a constant current of 286mA / g, the discharge capacity was the highest to 1428mAh / g, because the electrical conductivity is higher than in Example 6 and the phosphorus content is higher than in Examples 3 and 4 to be.
  • Example 7 The constant current charge and discharge curves of Example 7 are shown in FIG. 7. As shown in FIG. 7, the charge capacity of the first cycle is 1208 mAh / g, and the discharge capacity is 1016 mAh / g. Compared to Example 4, graphene was added to the electrode to decrease the capacity per weight, and the initial efficiency was 84%, which is similar to that of Example 4.
  • Example 8 The constant current charge and discharge curves of Example 8 are shown in FIG. 8.
  • the charge capacity of the first cycle is 1698 mAh / g and the discharge capacity is 1473 mAh / g, which shows an excellent effect with an initial efficiency of 86%. Capacity retention in the second cycle was also excellent.
  • Example 10 The constant current charge and discharge curves of Example 10 are shown in FIG. 18.
  • the first cycle had a charge capacity of 1730 mAh / g and a discharge capacity of 1350 mAh / g, which showed a high capacity despite the high phosphorus content and a relatively high initial efficiency of 78%.
  • the constant current charge / discharge curve of Example 11 is shown in FIG. 20.
  • the charge capacity of the first cycle was 1870mAh / g and the discharge capacity was 1492mAh / g, indicating a high capacity, and the initial efficiency was 80%, and it can be seen that the initial capacity is increased when ethylene carbonate is added.
  • Example 12 The constant current charge and discharge curves of Example 12 are shown in FIG. 22.
  • the charging capacity was 1670mAh / g and the discharge capacity was 1100mAh / g, which was a high capacity, and the initial efficiency was 66%, which was somewhat lower than that in Example 10.
  • Example 13 The constant current charge and discharge curves of Example 13 are shown in FIG. 24.
  • the charge capacity was 1730mAh / g and the discharge capacity was 1520mAh / g, showing a high capacity, and the initial efficiency was also very high at 88%.
  • TEGDME tetraethylene glycol dimethyl ether
  • Comparative Example 2 The constant current charge and discharge curves of Comparative Example 2 are shown in FIG. 9. As shown in Fig. 9, the charge capacity of the first cycle is 1718mAh / g, the discharge capacity is 250mAh / g, and the efficiency is very low, which is 15%. From the second cycle it can be seen that the charge and discharge capacity is drastically reduced. Comparative Example 2 seems to have a low initial efficiency because the volume is expanded and contracted during the initial charging and discharging process, and some phosphorus (P) is electrically isolated so that the stored sodium does not escape. This is because the electrical isolation becomes serious when phosphorus is not complexed with carbon.
  • P phosphorus
  • the reversible capacity of Comparative Example 3 was 347 mAh / g, and the reversible capacity of Comparative Example 4 was 115 mAh / g, since the phosphorus content mainly responsible for storing sodium in the phosphorus-carbon composite was low or absent. It can be seen that the discharge and storage capacity of sodium ions is significantly lowered and has a very low value capacity.
  • the electrochemical cell prepared in Example 3 was charged by the constant current and constant voltage method and discharged by the constant current method to measure the life characteristics of the battery, and the results are shown in FIG. 10.
  • the electrochemical cell prepared in Example 10 was charged in a constant current / constant voltage method and discharged in a constant current method to measure the life characteristics of the battery, and the results are shown in FIG. 19. There is a slight decrease in capacity up to the first 10 cycles, but there is no decrease in capacity even after 60 cycles. Rather, all of the initially reduced capacity is recovered to maintain a stable capacity. In view of this, it can be seen that the use of graphite in the preparation of the phosphorus-carbon composite anode active material can realize the excellent initial capacity and ensure a stable lifetime.
  • the electrochemical cell prepared in Example 11 was charged by the constant current and constant voltage method and discharged by the constant current method to measure the life characteristics of the battery, and the results are shown in FIG. 21. Not only did the initial capacity increase than that of Example 10, but the portion where the capacity decreases initially disappears and then the capacity continuously increases, and after 30 cycles, a capacity of 1700 mAh / g or more appears. When ethylene carbonate is added to the electrolyte, it can be seen that more stable and superior performance can be achieved.
  • the electrochemical cell prepared in Example 12 was charged by the constant current and constant voltage method and discharged by the constant current method to measure the life characteristics of the battery, and the results are shown in FIG. 23. Although the initial dose was somewhat low, all of the samples prepared in Example 9 had a stable cycle, and when NaPF 6 salt was used, the initial capacity was still excellent even though the initial dose was somewhat low.
  • Example 13 The electrochemical cell prepared in Example 13 was charged by the constant current and constant voltage method and discharged by the constant current method to measure the life characteristics of the battery, and the results are shown in FIG. 25. High initial efficiency and stable capacity are shown without decreasing initial capacity or gradual change of capacity. Therefore, it is stable when tetraethylene glycol dimethyl ether is used as solvent in electrolyte.
  • the electrochemical cell prepared in Example 3 was charged and discharged with a constant current, and X-ray diffraction analysis was performed by ex-situ method. A current of 143 mA / g was used in the 0.0-1.5 V (vs. Na / Na + ) voltage range.
  • the electrodes were stopped at 1.5V, and each electrode was prepared by decomposing an electrochemical cell in an argon glove box to obtain an electrode. This electrode was performed by adhering Kapton tape to a beryllium (Be) window.
  • Be beryllium
  • the experimental results are shown in FIG. 11.
  • the phosphorus-carbon composite which was in an amorphous phase before charging, showed no peak due to the charging progressing to 0.2V, but specific peaks corresponding to Na 3 P were observed in the diffraction pattern obtained by X-ray diffraction analysis after stopping charging at 0.0V. It was confirmed to be amorphous again in the X-ray diffraction pattern measured after discharging this to 1.5V. This result confirms that the phosphorus-carbon composite is changed to the crystalline Na 3 P phase which was amorphous during the charging process, and then restored to the amorphous phosphor again during the discharge process.
  • the rate characteristic results of the electrochemical cell prepared in Example 3 are shown in FIG.
  • Charging and discharging experiments were carried out in the voltage range of 0.0 ⁇ 1.5V (vs. Na / Na + ), and the current was charged while changing the magnitude of 143mA / g, 286mA / g, 571mA / g, 1430mA / g, 2860mA / g.
  • Over discharge was performed. 12 shows very high reversible capacity despite increasing charge and discharge currents, 91% capacity at 1430mA / g current compared to capacity at 143mA / g current, and 82 at 2860mA / g. A dose of% is shown.
  • FIG. 1 Velocity characteristic results of the electrochemical cell prepared in Example 10 are shown in FIG.
  • Charging and discharging experiments were conducted in the voltage range of 0.0 ⁇ 1.5V (vs. Na / Na + ), and the magnitude of current was 50mA / g, 100mA / g, 200mA / g, 300mA / g, 500mA / g, 1000mA / g
  • Charging and discharging were performed while changing to 2000 mA / g and 50 mA / g.
  • FIG. 1 Charging and discharging experiments were conducted in the voltage range of 0.0 ⁇ 1.5V (vs. Na / Na + ), and the magnitude of current was 50mA / g, 100mA / g, 200mA / g, 300mA / g, 500mA / g, 1000mA / g
  • Charging and discharging were performed while changing to 2000 mA / g and 50 mA
  • FIG. 27 Velocity characteristic results of the electrochemical cell prepared in Example 11 are shown in FIG. 27. Experimental conditions were performed in the same manner as in Example 10 above. It can be seen that the use of ethylene fluoride carbonate as an additive to the electrolyte improves the rate characteristic. Even at a current of 500 mA / g, a capacity of 1200 mAh / g or more is shown, indicating a capacity of 80% or more of the capacity at a low current of 50 mA / g.
  • Velocity characteristic results of the electrochemical cell prepared in Example 13 are shown in FIG. 29.
  • Experimental conditions were performed in the same manner as in Example 10 above. This shows little reduction in capacity even at a current of 500mA / g and a capacity of more than 1100mAh / g at a current of 1000mA / g.
  • a large capacity of 800 mAh / g or more is expressed, indicating a capacity of 60% or more compared to the capacity at a low current of 50 mA / g.
  • tetraethylene glycol dimethyl ether was used as the solvent of the electrolyte, the most excellent speed characteristics could be achieved.
  • the output material of the phosphorus-carbon composite is very excellent as the anode active material of the sodium secondary battery capable of rapid charging.

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Abstract

La présente invention concerne un matériau actif d'anode pour un accumulateur au sodium, une électrode l'utilisant et un accumulateur au sodium le comprenant. Le matériau actif d'anode pour un accumulateur au sodium selon la présente invention est caractérisé en ce qu'il comprend un composite phosphore-carbone, le composite phosphore-carbone étant au moins un élément parmi le phosphore rouge, le phosphore noir, le phosphore blanc, et le phosphore jaune.
PCT/KR2014/001220 2013-02-15 2014-02-14 Matériau actif d'anode pour accumulateur au sodium, procédé de fabrication d'électrode l'utilisant et accumulateur au sodium le comprenant Ceased WO2014126413A1 (fr)

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CN108767209A (zh) * 2018-04-26 2018-11-06 昆明理工大学 一种磷/多孔碳/石墨烯复合材料的制备方法
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