US20050207966A1 - Surface preparation of natural graphite and the effect of impurities on grinding and the particle distribution - Google Patents

Surface preparation of natural graphite and the effect of impurities on grinding and the particle distribution Download PDF

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US20050207966A1
US20050207966A1 US10/204,715 US20471503A US2005207966A1 US 20050207966 A1 US20050207966 A1 US 20050207966A1 US 20471503 A US20471503 A US 20471503A US 2005207966 A1 US2005207966 A1 US 2005207966A1
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graphite
process according
particles
purification
impurities
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Karim Zaghib
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Hydro Quebec
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Priority claimed from CA002307118A external-priority patent/CA2307118A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 the physical and chemical purification specific to the mineral of natural graphite with the goal of generating a purified graphite which is particularly advantageous for use in carbon-lithium anodes.
  • This purification is applied preferentially to the surface of natural graphite to permit the formation of a passivating layer with the first electrical discharge or insertion of lithium in the graphite when the graphite is used in a lithium-ion battery. Grinding to a very small size before the purification permits the optimisation of the size distribution of the particles, which gives rise to an electrode which is much more homogenous.
  • the negative carbon-lithium electrode has recently caused a great deal of interest in the industrial but also in the scientific community.
  • the use of such an electrode in a rechargeable battery resolves the crucial problem of lithium metallic electrodes which are poorly recharged in liquid electrolytes because of the growth of dendrites once the charged density (C/cm 2 ) and/or the current density (mA/cm 2 ) exceed limiting values for the good operation of the battery.
  • This major problem has slowed the arrival of lithium batteries in the classical formats (AA, C, D, etc.) to the public at large.
  • the first such type of battery was commercialised at the beginning of the 1990s by Sony Energytech. This battery is said to be a lithium-ion and consists of a negative electrode made of carbon-lithium.
  • the operating principle of this electrode resides in the reversible insertion of lithium between layers of carbon. These layers are characterized by very strong anisotropic connective carbon-carbon forces within the layers (very strong covalent bonds) and between layers (very weak Van der Waals forces). Thus, because lithium is a very weak cation, it may rapidly diffuse between 2 D layers, forming bonds of the ionic type between layers without involving irreversible changes of the bonds within the layers. Only a slight spacing between layers is observed, thus accommodating the inserted lithium.
  • U.S. Pat. No. 5,756,062 discloses the modification of the surface of a high purity graphite.
  • the graphite is not however one obtained directly from the mineral.
  • the chemical modification of the graphite is performed by fluorine, chlorine or phosphorous treatment.
  • the graphite used conventionally as electrode material in a lithium-ion battery is generally obtained from two distinct sources: synthetic graphite or natural thermally highly purified graphite, preferably treated at temperatures higher than 2,500° C.
  • This type of graphite although of excellent quality, is however very costly, and this has a direct impact on the cost of the final product eventually sold in the market.
  • the graphite is only reduced to the powder state after having been purified or synthesised, this causes certain problems during the grinding process. In effect, the uniformity of the size distribution of the particles in the powder is markedly altered, since pure graphite is very fragile. In fact, it can be said that the distribution is non-uniform.
  • the graphite particles produced by the process of the invention have a size varying from 1 to 50 ⁇ m and are generally free of impurities and sites of corrosion. Preferably they have the following properties:
  • the invention also relates to a carbon metal anode, preferably lithium, based on a natural graphite obtained by the previously described process.
  • a carbon metal anode preferably lithium
  • Such an anode is particularly advantageous in an electrochemical battery such as a lithium-ion type.
  • a purified graphite comprising particles having an external surface substantially stripped of impurities and sites of corrosion having an electric conductivity, used for a number of commercial applications.
  • a new method has been developed to produce a purified graphite in the form of small particles which can be used in an electrochemical battery, for example, of the lithium-ion type, while maintaining a relatively uniform particle size distribution.
  • This type of graphite which can equally be used in other applications, such as an electric conductor in a cathode (batteries) or fuel cells, or in the field of cars (breaks and joints) or in the nuclear field.
  • the present invention relates to a purification method, either chemical or physical, of impurities found on the surface of the natural graphite, i.e. where the passivating film is formed.
  • the present method permits the removal of the impurities which can harm the formation of the passivating film and the cycling of the carbon-lithium anode.
  • the grinding process is advantageously conducted before purification, this permits a better control of the size and the size distribution of the particles, where a more uniform powder does not require filtration to remove the oversized and undersized particles.
  • the subsequent purification step essentially seeks to remove impurities from the surface of the graphite particles which generate an electric conductivity, such as compounds comprising silica oxide and iron. Those compounds also cause the doping or the reduction by lithium of the compounds in which they are found. These phenomena should not be present or at least minimised in the passivating layer which will be formed at the surface of the electrode, because they will cause the degradation of the batteries efficiency, and ultimately a short circuit.
  • the presence of surface impurities favouring ionic conductivity, such as calcium fluoride have no negative impact on the graphite electrode performance, because they have a strong ionic character less favourable to electronic conductivity.
  • the impurities present in graphite a mineral are generally the following (in descending order of priority): Si>Ca>Fe>Mg>S>Al.
  • these compounds containing silica must be eliminated, on one hand because lithium reduces or dopes compounds containing silica (such as SiO 2 , SiO and Si metal), and on the other hand these compounds of silicium are electronic conductors. This last property is completely incompatible with the properties of the passivating film, which represents a key element to a good carbon-lithium anode which is characterized by a long lifespan.
  • an acid treatment is used, for example with H 2 SO 4 , HNO 3 , HCl, HF or their mixtures thereof
  • a treatment with HF or a fluoridated derivative allowing the generation of HF in the medium represents a particularly preferred embodiment.
  • This treatment equally causes an interaction between the fluoride and the calcium already present in the mineral, leading to the formation of calcium fluoride, a compound which is strongly ionic, an electric insulator as well as a good anionic conductor at high temperatures.
  • the presence of calcium fluoride will not alter the formation of the passivating layer.
  • the present method of purification does not change the size of the particles produced by the grinding process. There is no agglomeration of particles, which are free and which may produce an homogenous mixture with the binder in order to produce an electrode of good quality (roughness, thickness, porosity, etc.).
  • a graphite mineral from StratminGraphite (Lac des furs—Québec), of a particle size about 375 ⁇ m was used. The particles were first ground until their size varied between 1 and 50 ⁇ m. It should be noted that once the particle size is less than 1 ⁇ m, the graphite loses its crystallinity and the term intercalation of lithium becomes doping.
  • the grinding process can be done by any method known to the person skilled in the art. These techniques include jet milling, air milling, ball milling, etc.
  • the purification step by thermal means can be accomplished by conventional means, i.e., in a furnace and at a sufficiently high temperature to allow the vaporisation of all impurities typically between 1,000 and 3,100° C.
  • the purification step by chemical means can be accomplished by different methods using acid compounds containing fluorine, nitrate, sulphate and chloride or basic compounds such as potassium or sodium hydroxide, in order to clean the surface of the graphite and to permit the subsequent formation of a stable passivating film at the time of the reduction of the electrolyte and during the first insertion of lithium in the graphite.
  • the purification method by chemical means can comprise:
  • the concentration of HF or of fluoridated derivatives added for the purification has to be preferably between 10% and 50% (by weight) and at a process temperature which preferably does not exceed 250° C. in order to maximise the output.
  • the concentration of this acid will vary preferably between 10 and 30%.
  • the graphite is milled by air milling, until the particles attain a size of approximately 201 ⁇ m.
  • the impurities are then separated by flotation.
  • FIG. 1 is a diagram of the conventional method
  • FIG. 2 is a diagram of the method according to the invention.
  • FIG. 3 illustrates the formation of an anode from graphite particles obtained according to the method of this invention
  • FIG. 4 illustrates a particle of graphite according to the invention formed from several crystallites
  • FIG. 5 illustrates the exfoliation of graphite in a particle according to the invention.
  • FIG. 3 illustrates the formation of an anode with particles of graphite obtained according to the method of the invention, which are deposited on a collector. During reduction, there is the formation of a passivating film, which is at the same time an ionic inductor, and electronic isolator, which represent ideal conditions for electrochemistry.
  • FIG. 4 shows that the graphite particle according to the invention is constituted by a group of crystallites.
  • the Lc is controlled. In this case, very strong acids have been used for the purification, the Lc becomes very small and graphite illustrated in FIG. 5 is obtained.
  • a natural graphite having an initial particle size of 375 ⁇ m is ground by a process of air milling until the particle size reaches 10 ⁇ m.
  • the size of the main particles obtained (50% distribution of particles or D50%) is 10.52 ⁇ m.
  • the Gaussian distribution of graphite has only one maximum and no additional peak.
  • the granulometric distribution was determined with the aide of a MicrotracTM particle analyser built and sold by Leeds & Northrul.
  • the methanol was used as the carrier fluid.
  • the ground graphite was leached in an aqueous bath of 30% HF. The temperature of the mixture is maintained at 90° C., with a leached time of 180 minutes.
  • the graphite is then filtered, washed with copious amounts of water, and the powder dried for a period of 24 hours at 120° C.
  • the graphite powder obtained is analysed by reversed diffusion coupled with EDX (Energy Dispersive X-ray). No exfoliation of the particles was observed. In addition the analysis by EDX shows that the majority of the impurities remaining are constituted by calcium. The purity of this sample is 99.6%, as obtained by the analysis of the impurities found in the ashes after incineration.
  • EDX Electronic Dispersive X-ray
  • the graphite is mixed with a binder of polyvinylidene fluoride (PVDF) (Kruha: KF-1700) and with N-methylpyrolidone in a mass ratio of 90:10.
  • PVDF polyvinylidene fluoride
  • N-methylpyrolidone in a mass ratio of 90:10.
  • the mixture is then applied to a collector of copper by the method of Doctor BladeTM.
  • the graphite electrode thus obtained is dried under vacuum at 120° C. for 24 hours.
  • the said electrode is placed in a button size battery of type 2035 (diameter 20 mm, thickness 3,5 mm).
  • a CelgardTM separator 2300 soaked in electrolyte 1M LiPF 6 +EC/DMC: 50/50 (ethylene carbonate+dimethylcarbonate) is used.
  • the metallic lithium is used as a reference and a counter-electrode.
  • the electrochemical tests were conducted at ambient temperature. The discharge and charge curves were obtained between 0 V and 2.5 V in C/24.
  • the first coulombic output is 85%, which is superior to commercial graphite used in lithium-ion batteries (typically 81%).
  • Natural graphite having an initial particle size of 375 ⁇ m is ground by a process of air-milling until the particles attain a size of 10 ⁇ m.
  • the graphite is then leached in a mixed aqueous bath comprising 30% H 2 SO 4 and 30% HF. 106.5 ml of the mixed acid is heated to 90° C., and 30 g of graphite is then added into the solution.
  • the graphite is leached for 180 minutes in a reactor.
  • the solid is then filtered, washed with copious amounts of water, and dried at 120° C. for 24 hours.
  • the size (D50%) is 10.92 ⁇ m, and this before and after purification.
  • the Gaussian distribution for the graphite has only one single maximum without any peak.
  • the coulombic efficiency of the first cycle is 90%.
  • the irreversible plateau caused by the passivating layer is formed normally near 800 mV. This means that the elements Ca, F or CaF 2 have no influence on the formation of the passivating film.
  • the natural graphite used in this example is processed in an identical manner as that described in Example 2, with the exception that the HF concentration is now 20%.
  • Analysis of the impurities in the graphite by EDX shows the main presence of the elements Ca and F.
  • the analysis of the impurities of the residual ashes shows the graphite to have a purity of 99.75%.
  • the preparation of the electrode and the electrochemical tests were conducted with the identical procedures described in example 1.
  • the coulombic efficiency of the first cycle is 89%.
  • the irreversible plateau due to the passivating layer is formed normally near 800 mV.
  • the natural graphite used in this example is processed in an identical manner as that described in Example 2, with the exception that the concentration of HF is of 10%.
  • the preparation of the electrode and the electrochemical test are identical to the procedures described in Example 1.
  • the coulombic efficiency of the first cycle is 75%.
  • the irreversible capacity of 106.7 mAh/g is very high compared to that of the graphite in Examples 2 and 3, which were leached respectively in HF 30% and HF 20%.
  • the natural graphite used in this example is processed in an identical manner as that described in Example 2, with the exception of the H 2 SO 4 —HF mixture wherein HF is replaced by NH 4 F, also present in the concentration of 30%.
  • the coulombic efficiency of the first cycle is 90%.
  • the irreversible capacity of the graphite is 44 mAh/g.
  • the natural graphite used in this example is processed in an identical manner as described in Example 2 with the exception that in the H 2 SO 4 —HF mixture HF is replaced by NH 4 F, HF (NH 5 F 2 ) at a concentration of 30%.
  • the analysis of impurities of the graphite by EDX shows the presence, in majority, of Ca and F.
  • the analysis of the impurities of the residual ashes shows the graphite to have a purity of 99.57%.
  • the preparation of the electrode and the electrochemical tests are identical to those described in Example 1.
  • the coulombic efficiency of the first cycle is 88%.
  • the irreversible capacity is 49 mAh/g.
  • a natural graphite having an initial particle size of 375 ⁇ m is ground by a process of air-milling until the particles achieve a size of 10 ⁇ m.
  • the graphite is leached in two steps. Initially, with an aqueous solution of 30% HCl, followed by an aqueous solution of 30% HF. For each leach step, 106.5 ml of acid solution is heated to 90° C., and 30 g of graphite are added. The graphite is leached for 180 minutes in a reactor. The solid is filtered, washed with copious amounts of water and dried at 120° C. for 24 hours.
  • the size (D50%) is 10.02 ⁇ m.
  • the Gaussian distribution of graphite has a single maximum with no flattening.
  • the coulombic efficiency of the first cycle is 88%.
  • the irreversible plateau of the passivating layer is normally formed at 800 mV.
  • the natural graphite used in this example was processed in the same manner identical to that described in Example 7 but replacing HCl with HNO 3 .
  • the size (D50%) of graphite is 10.26 ⁇ m.
  • the Gaussian distribution of the graphite has only one maximum and no additional peak.
  • the coulombic efficiency of the first cycle is 86%.
  • the irreversible plateau of the passivating layer is formed normally near 800 mV, which confirms that the elements Ca and Mg have no influence on the formation of the passivating layer.
  • the natural graphite used for this example is processed in the same manner as that described in Example 7 with HCl being replaced by a base notably KOH, at a concentration of 30%.
  • the analysis of the impurities of graphite by EDX shows the presence of the elements Ca and F.
  • the analysis of impurities found in the residual ashes shows the graphite to have a purity of 99.77%.
  • the coulombic efficiency of the first cycle is 88%.
  • a graphite comprising particles of 375 ⁇ m is initially purified in a bath of HF according to the following procedure. 106.5 ml of acid are heated to 90° C., and 30 g of graphite are added. The graphite is leached for 180 minutes in the reactor. The solid is then filtered, washed with copious amounts of water and dried at 120° C. for 24 hours.
  • the graphite is ground until the particle size reaches 10 ⁇ m by the procedure previously described.
  • the size (D50%) is 10.67 ⁇ m.
  • the distribution of graphite has two maxima with a flattening of the level at a size>18 ⁇ m. It is well known that this type of distribution is less favourable to the optimal functioning of carbon-lithium anodes, and illustrates the better uniformity of natural graphite ground before its purification.
  • the coulombic efficiency of the first cycle is 75%.
  • the value of 110 mAh/g of the irreversible capacity is high due to its purity (99.43%) and its elevated specific surface (7.08 m 2 /g).
  • the graphite used in this example is prepared according to the method of Example 10. The conditions of purification and grinding are the same as used in Example 7.
  • the size (D50%) of the graphite particles is 12.40 ⁇ m.
  • the distribution has two maxima, the first at 10 ⁇ m, and the second at 17.7 ⁇ m.
  • the coulombic efficiency of the first cycle is 86%.
  • the irreversible capacity is 59 mAh/g.
  • the natural graphite used in this example is processed in a manner identical to that of Example 11 but replacing HCl for HNO 3 .
  • the particle size (D50%) of the graphite is 12.11 ⁇ m.
  • the distribution has two maxima, a first at 8 ⁇ m and a second at 18 ⁇ m.
  • the analysis of impurities in the graphite by EDX shows the presence of Ca.
  • the analysis of the impurities found in the residual ashes shows the graphite to have a purity of 99.99%.
  • the preparation of the electrode and the electrochemical tests are identical to the procedures described in Example 0.1.
  • the coulombic efficiency of the first cycle is 88%.
  • the irreversible capacity is 56 mAh/g.
  • the initial size of graphite is taken from 375 ⁇ m to 10 ⁇ m by a process of grinding.
  • the graphite is then subjected to a thermal treatment at high temperature (2,800° C.) for 2 hours.
  • the analysis of the impurities in the graphite by EDX shows the absence of these.
  • the coulombic efficiency of the first cycle is 87%.
  • the irreversible capacity is 54.7 mAh/g.
  • natural Chinese graphite having a higher Si content but a lower content of Ca than graphite from StratminGraphite.
  • the coulombic efficiency of the first cycle is 88%.
  • This purification process allows the control of the interplanar distance L c ( FIG. 3 ). In the field of lithium-ion batteries, the control of this parameter minimises the co-insertion of solvent and stabilises the passivating film.
  • a natural graphite of Brazilian origin (table 1) having an initial particle size of 323 ⁇ m is ground by a process of air-milling until the particles reach a size of 20 ⁇ m.
  • This powder is processed in a manner identical to that described in Example 5, with a H 2 SO 4 —NH 4 F mixture at a concentration of 30%.
  • the analysis of the impurities found in the residual ashes show the graphite to have a purity of 99.99%.
  • the specific surface is 4.285 m 2 /g.
  • the preparation of the electrode and the electrochemical tests are identical to the procedures described in Example 1.
  • the coulombic efficiency of the first cycle is 91.0%.
  • the irreversible capacity of the graphite is 37 mAh/g.
  • a natural graphite from Lac Knife (Quebec, Canada) (table 2) having an initial particle size of 323 ⁇ m is ground by an air-milling process until the particles reach a size of 20 ⁇ m whereas the level of oxygen is 1.9%.
  • the powder is processed in an identical manner to that described in Example 5, with a H 2 SO 4 —NH 4 F mixture at a concentration of 30%. After leaching, the level of oxygen is reduced to 0.18%. It is clear that the process according to the invention greatly reduces the level of oxygen.
  • the analysis of the impurities found in the residual ashes shows the graphite to have a purity of 99.24%.
  • the specific surface is 2.696 m 2 /g.
  • the preparation of the electrode and the electrochemical tests are identical to the procedures described in Example 1.
  • the coulombic efficiency of the first cycle is 91%.
  • the irreversible capacity of the graphite is 36 mAh/g.
  • the natural graphite used in this example is identical to that used in Example 15. It was processed in an identical manner as that described in Example 5 however replacing the H 2 SO 4 with HCl.
  • the coulombic efficiency of the first cycle is 89.4%.
  • the irreversible capacity of the graphite is 43 mAh/g.
  • the natural graphite used in this example is identical to that used in Example 15 with an average particle size of 10 ⁇ m.
  • the graphite is leached in a bath with an aqueous mixture comprising 150 ml of HCl (30%) and 1.0 g of CaF 2 .
  • the mixture is heated to 90° C., and 20 g of graphite are added to the solution.
  • the graphite is leached for 180 minutes in a reactor.
  • the solid is then filtered, washed with copious amounts of water and dried at 120° C. for 24 hours.
  • the coulombic efficiency of the first cycle is 85%.
  • the irreversible capacity of the graphite is 64 mAh/g.
  • the natural graphite used in this example is identical to that used in Example 18.
  • the natural graphite is processed in the same manner as described in Example 18 but replacing HCl with H 2 SO 4 (30%) and CaF 2 by 1.5 g of LiF.
  • the coulombic efficiency of the first cycle is 82%.
  • the irreversible capacity of the graphite is 77.5 mAh/g.

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CA002299626A CA2299626A1 (fr) 2000-02-25 2000-02-25 Purification en surface du graphite naturel et utilisation du graphite purifie dans une anode carbone-lithium
CA2,299,626 2000-02-25
CA2,307,118 2000-04-28
CA002307118A CA2307118A1 (fr) 2000-04-28 2000-04-28 Purification en surface du graphite naturel et utilisation du graphite purifie dans une anode carbone-lithium
PCT/CA2001/000233 WO2001062666A1 (fr) 2000-02-25 2001-02-23 Purification en surface du graphite naturel et effet des impuretes sur le broyage et la distribution granulometrique

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US20040053050A1 (en) * 2000-10-25 2004-03-18 Abdelbast Guerfi Potato-shaped graphite particles with low impurity rate at the surface, method for preparing same
US20070077495A1 (en) * 2005-10-05 2007-04-05 California Institute Of Technology Subfluorinated Graphite Fluorides as Electrode Materials
US20070218364A1 (en) * 2005-10-05 2007-09-20 Whitacre Jay F Low temperature electrochemical cell
US20080171268A1 (en) * 2006-08-11 2008-07-17 Rachid Yazami Dissociating agents, formulations and methods providing enhanced solubility of fluorides
US20090111021A1 (en) * 2007-03-14 2009-04-30 Rachid Yazami High discharge rate batteries
US7537682B2 (en) 2004-03-17 2009-05-26 California Institute Of Technology Methods for purifying carbon materials
US7794880B2 (en) 2005-11-16 2010-09-14 California Institute Of Technology Fluorination of multi-layered carbon nanomaterials
US20110195313A1 (en) * 2008-10-10 2011-08-11 Sung Man Lee Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery comprising the same
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US8377586B2 (en) 2005-10-05 2013-02-19 California Institute Of Technology Fluoride ion electrochemical cell
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JP6783505B2 (ja) * 2014-07-18 2020-11-11 積水化学工業株式会社 薄片化黒鉛、電極材料及び薄片化黒鉛−樹脂複合材料
KR102460964B1 (ko) * 2015-12-03 2022-10-31 삼성에스디아이 주식회사 탄소재, 이를 포함하는 음극 활물질, 상기 음극 활물질을 포함하는 리튬 전지, 및 상기 탄소재의 제조방법
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US20100092808A1 (en) * 2000-10-25 2010-04-15 Hydro Quebec Potato-Shaped Graphite Particles with Low impurity Rate at the Surface, Method for Preparing the Same
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US20120070733A1 (en) * 2009-02-20 2012-03-22 Mitsubishi Chemical Corporation Carbon material for lithium ion secondary battery
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US8647776B2 (en) * 2009-02-20 2014-02-11 Mitsubishi Chemical Corporation Carbon material for lithium ion secondary battery
CN103109403A (zh) * 2010-09-16 2013-05-15 电子部品研究院 阳极活性材料、包括该阳极活性材料的非水性锂二次电池及其制备方法
WO2012036372A2 (ko) * 2010-09-16 2012-03-22 전자부품연구원 음극 활물질, 그를 갖는 비수계 리튬이차전지 및 그의 제조 방법
WO2012036372A3 (ko) * 2010-09-16 2012-05-10 전자부품연구원 음극 활물질, 그를 갖는 비수계 리튬이차전지 및 그의 제조 방법
US8932763B2 (en) 2010-09-16 2015-01-13 Korea Electronics Technology Institute Anode active material, non-aqueous lithium secondary battery including the same, and manufacturing method thereof
CN104271500A (zh) * 2012-06-29 2015-01-07 海洋王照明科技股份有限公司 一种石墨烯薄膜及其制备方法和用途
WO2017027731A1 (en) * 2015-08-11 2017-02-16 Metoxs Pte Ltd Method for cost-efficient industrial production of graphite oxide, graphene oxide and graphene
CN108473318A (zh) * 2015-08-11 2018-08-31 梅多克斯私人投资有限公司 氧化石墨、氧化石墨烯和石墨烯的经济实用的工业生产方法
US10710094B2 (en) 2016-05-18 2020-07-14 Syrah Resources Ltd. Method and system for precision spheroidisation of graphite
US11000857B2 (en) 2016-05-18 2021-05-11 Syrah Resources Ltd. Method and system for precision spheroidisation of graphite
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US10710882B2 (en) * 2016-06-27 2020-07-14 Syrah Resources Ltd. Purification process modeled for shape modified natural graphite particles

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