US20040053050A1 - Potato-shaped graphite particles with low impurity rate at the surface, method for preparing same - Google Patents
Potato-shaped graphite particles with low impurity rate at the surface, method for preparing same Download PDFInfo
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- US20040053050A1 US20040053050A1 US10/381,843 US38184303A US2004053050A1 US 20040053050 A1 US20040053050 A1 US 20040053050A1 US 38184303 A US38184303 A US 38184303A US 2004053050 A1 US2004053050 A1 US 2004053050A1
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Definitions
- the present invention relates to modified graphite particles and to particles based on graphite that are also characterized in that they have a potatolike shape.
- the present invention also concerns processes that make it possible to prepare these new particles, as well as the use of the particles thus obtained in particular as moisture absorbers and/or oxygen absorbers. These processes can be monitored by controlling the values obtained from the mathematical functions that are characteristic of the shape of the crystalline (edge, basal, Lc and La) and geometric structures of the graphite.
- These new particles also exhibit, within the scope of an electrochemical application, improved stability to cycling by increasing, on one hand, the density of the electrode and on the other, the diffusion kinetics of the intercaling material (Li, Na or other).
- the performances of the anode depend on the type of graphite and the physical shape of these particles.
- the efficiency of the first intercalation of the ion in graphite is dependent on the specific surface area and the edge surface fraction (K. Zaghib et al, J. Electrochemical Soc. 147 (6) 2110 to 2115, 2000).
- a low specific surface area is associated with a lower contribution of passivation film.
- Natural graphite is found exclusively in the form of flakes, while artificial graphite can be found in the form of flakes, fibers or spheres.
- the flake shape has an elevated degree of preferential orientation which will induce anisotropy in the electrode. An orientation such as this reduces the intercalation kinetics of lithium across the edges.
- the only spherical carbon available on the market is Mesocarbon Microbeads MCMB processed at 2,800° C. by Osaka Gas (T. Kasuh et al., J. Power Source 68 (1997), 99).
- This carbon is an artificial graphite that requires costly processing at high temperature to be ordered, as well as complex synthesis that can increase its production cost.
- the maximum reversible capacity obtained with this artificial graphite is of the order of 280 mAh/g, which is low in comparison to the corresponding capacity of natural graphite, which is 372 mAh/g.
- the present invention especially concerns potatolike shaped modified graphite particles having impurities in their internal structure and having on the surface a low, even nil, rate of an impurity or several impurities, in particular the impurities usually present in natural graphites.
- the present invention also relates to particles based on modified graphite made up of prismatic graphite particles covered with a metallic deposit and/or a carbonic deposit.
- the graphite particles according to the present invention can be used, in particular, as humidity absorbers and/or oxygen absorbers and, especially because of their cycling performance, can be used in the manufacture of negative electrodes, preferably in the manufacture of negative electrodes for rechargeable electrochemical generators.
- the present invention also concerns methods that make possible the preparation of these particles and the preparation of electrodes containing them.
- FIG. 1/ 15 According to model 1, transformation of the prismatic particles into spherical particles by decreasing the fb and increasing the fe. This transformation can be carried out using several techniques: jet mill, attrition, ball mill, hammer mill, CF mill or atomizer mill, planetary mixer, hybridizer.
- FIG. 2/ 15 According to model 2, transformation of the cylindrical particles into spherical particles by decreasing the fb and increasing the fe. This transformation can be carried out using several techniques: jet mill, attrition, ball mill, hammer mill, CF mill or atomizer mill, planetary mixer, hybridizer.
- FIG. 3/ 15 According to model 1, the prismatic-shaped artificial or natural graphite, in the presence of its impurities and, soluble agents of the NaCl and NH 4 F type or the like (preferably with spherical shape), is transformed into spherical-shaped graphite by decreasing the basal fraction (fb) and increasing the edge fraction (fe). This transformation can be carried out using several techniques: jet mill, attrition, ball mill, hammer mill, CF mill or atomizer mill, planetary mixer, hybridizer.
- FIG. 4/ 15 According to model 2, the carbon fiber, the cylindrical-shaped artificial or natural graphite, in the presence of its impurities and soluble agents of the NaCl and NH 4 F type or the like (preferably with spherical shape), is transformed into spherical-shaped graphite by decreasing the basal fraction (fb) and increasing the edge fraction (fe). This transformation can be carried out using several techniques: jet mill, attrition, ball mill, hammer mill, CF mill or atomizer mill, planetary mixer, hybridizer.
- FIG. 5/ 15 According to model 1, the prismatic-shaped artificial or natural graphite, in the presence of its impurities and non-soluble agents of the SiO 2 and TiO 2 type, ceramic, material, hard compound or the like (preferably with spherical shape) is transformed into spherical-shaped graphite by decreasing the basal fraction (fb) and increasing the edge fraction (fe).
- This transformation can be carried out using several techniques: jet mill, attrition, ball mill, hammer mill, CF mill or atomizer mill, planetary mixer, hybridizer.
- FIG. 6/ 15 According to model 2, the cylindrical-shaped artificial or natural graphite, in the presence of its impurities and non-soluble agents of the SiO 2 and TiO 2 type, ceramic material, hard compound or the like (preferably with spherical shape), is transformed into spherical-shaped graphite by decreasing the basal fraction (fb) and increasing the edge fraction (fe) This transformation can be carried out using several techniques: jet mill, attrition, ball mill, hammer mill, CF mill or atomizer mill, planetary mixer, hybridizer.
- FIG. 7/ 15 Comparative modeling between the prismatic and cylindrical model for two types of particles of 2 and 40 ⁇ m.
- FIG. 8/ 15 Graphite particles before attrition.
- FIG. 9/ 15 Graphite particles after attrition.
- FIG. 10/ 15 Electrochemical results of natural graphite NG20, after attrition.
- FIG. 11/ 15 Electrochemical results with commercial spherical graphite MCMB.
- FIG. 12/ 15 Scanning electron microscope micrograph showing the potatolike shape of a 12 ⁇ m particle obtained in example 3, according to the invention.
- FIG. 13/ 15 Scanning electron microscope (MEB) micrograph showing the trend in basal and edge. functions for a graphite particle conforming to mathematical model 1.
- FIG. 14/ 15 Scanning electron microscope micrograph showing the potato shape of a 12 im graphite particle obtained in example 3.
- FIG. 15/ 15 Micrograph of a particle obtained in example 3, micrographed with the scanning electron microscope (MEB), showing that the basal function (fb) decreases and the function (fe) increases.
- a first object of the present invention comprises modified graphite particles obtained from graphite (preferably from synthetic graphite), the structural parameters of said particles corresponding to at least one of the equations
- B represents the length of the particle in ⁇ m
- T represents the thickness of the particle in ⁇ m.
- a tap density measured according to the method associated with the instrument sold under the name of Logan Instrument Corp. Model Tap-2, between 0.3 and 1.5, preferably between 0.5 and 1.4, most preferably between 1 and 1.3 g/cc; and
- a second object of the present invention comprises modified graphite particles obtained from graphite, said particles having a potatolike shape, comprising impurities in their internal structure and having on the surface a rate of one or more impurities, measured according to the retrodiffused detector method defined in the publication Kimoto S. and Hashimoto H., (1966), in Electron Microphone, John Wiley, New York, page 480 and in Gedcke, D. A., Ayers, J. B. and DeNee, P. B. (1978),SEM/1978, SEM Inc, AMF O'Hare, Ill., page 581, that is less than 10%, which preferably varies between 2% and 4%, and said particles also having at least one of the following three characteristics:
- a tap density measured according to the previously identified method between 0.3 and 1.5, preferably between 0.5 and 1.4, most preferably between 1 and 1.3 g/cc;
- particles preferably potatolike shape, most preferably spherical
- the mass of these particles of NaCl and/or of NH 4 F represents 1 to 4% of the total mass of the modified graphite particles.
- the rate of impurities on the surface of graphite may be reduced in different ways; one particularly effective method is the one described in the application PCT/CA100233 held by the Hydro-Quebec Company. The contents of this document are incorporated in the present application by reference.
- a preferred sub-family of the particles according to the second object of the present application is made up of modified graphite particles for which TGA analysis carried out according to the method associated with the device sold under the name TGA/DTA Model SDT 2960, TA Instruments Inc., New Castle, Del., gives an initial temperature value between 560 and 660 degrees Celsius, associated with the loss of weight, as is illustrated in FIG. 11/ 11 .
- the particle parts of graphite modified according to the invention may contain impurities, for example, at least one impurity from the group made up of the chemical elements Fe, Mo, Sb, As, V, Cr, Cu, Ni, Pb, Co, Ca, Al, Ge, Si, Ba, Be, Cd, Ce, Co, Ciu, Dy, Eu, La, Li, Mo, Nd, Ni, Pb and Pr.
- impurities for example, at least one impurity from the group made up of the chemical elements Fe, Mo, Sb, As, V, Cr, Cu, Ni, Pb, Co, Ca, Al, Ge, Si, Ba, Be, Cd, Ce, Co, Ciu, Dy, Eu, La, Li, Mo, Nd, Ni, Pb and Pr.
- One preferred sub-family among the graphite particles according to the invention is made up of particles in which the percentage of impurities by weight present in the said particles, expressed with respect to the total mass of modified graphite particles and measured according to the ash method, is between 1 and 10%, and preferably between 2 and 4%.
- a third object of the present invention comprises modified graphite particles obtained from graphite, said particles having a potatolike shape and containing from 5 to 20% of at least one of the following compounds SiO 2 , MgO, ceramic compounds or a mixture of these, said compounds preferably being attached to the modified graphite particles by physical forces and having at least one of the following three characteristics:
- a tap density measured according to the previously described method between 0.3 and 1.5, preferably between 0.4 and 1.4, most preferably between 1 and 1.3 g/cc;
- a granulometric dispersion measured according to the previously defined method such that the D90/D10 ratio varies between 2 and 5 for particles with a size between 1 and 50 ⁇ m, preferably such that the D90/D10 ratio varies between 2.2 and 4.2 for particles having a size between 2 and 30 ⁇ m;
- particles preferably potatolike shaped, most preferably spherical
- the mass of these particles of NaCl and/or of NH 4 F represents 1 to 10% of the total weight of the modified graphite particles.
- One particularly advantageous family of graphite particles according to the present invention is made up of all the modified graphite particles in which the interplane distance d 002 (measured according to the method associated with the diffractometer sold under the name XRD Analysis Siemens Model D500 Diffractometer) varies from 33 to 3.4 angstroms and/or the BET (measured using the method associated with the device Quantachrome Autosorb automated gas adsorption system using N 2 ) varies between 0.5 g/m 2 and 50 g/m 2 .
- modified graphite particles of the invention those having a cycling stability greater than 500 cycles are of particular interest in the scope of electrochemical applications.
- the reduction of the basal function and the increase of the edge function, preferably the rounding of the particles is carried out using a means of attrition, said means preferably being made up of balls such as steel balls, ceramic balls or a mixture of steel and ceramic balls.
- a fifth object of the present invention comprises a process for preparing modified graphite particles according to claim 1 or 2, preferably from natural graphite, comprising at least the following two steps:
- the graphite particles used at the beginning of the process have a size between 1 and 450 ⁇ m, preferably between 2 and 350 ⁇ m.
- the attrition process is carried out in the presence of an additive, preferably an additive of the metallic oxide type such as SiO 2 , TiO 2 , ZrO 2 , and preferably in the presence of steel balls, ceramic balls or in the presence of a mixture of steel and ceramic balls.
- an additive preferably an additive of the metallic oxide type such as SiO 2 , TiO 2 , ZrO 2 , and preferably in the presence of steel balls, ceramic balls or in the presence of a mixture of steel and ceramic balls.
- a preferred variation comprises using the method according to the invention under conditions such that at least one of the two steps is carried out in a controlled atmosphere or in air, the controlled atmosphere preferably being based on nitrogen, argon, helium or a mixture of these gases.
- Step i) can be a hybrid step using both jet milling and attrition, the attrition preferably being carried out after jet milling is used.
- step i) of the method is carried out using jet milling.
- a sixth object of the present invention comprises modified graphite particles such as defined above and below, as moisture sensors and/or oxygen absorbers.
- a seventh object of the present invention comprises negative electrodes, preferably negative electrodes for a rechargeable electrochemical generator prepared with a bonding agent, preferably a bonding agent of the PVDF or PTFE type, and with graphite particles according to any one of the objects of the present invention.
- An eighth object of the present invention is made up of a process for preparing an electrode for a rechargeable generator based on graphite particles according to the present invention or based on graphite particles such as those obtained by a method according to the invention, comprising at least the following steps:
- a—solubilization of at least one bonding agent preferably selected from the group comprising PVDF, PTFE
- a solvent preferably in a strong solvent selected from the group comprising NMP (N-methylpyrrolidone), cyclopentanone at the highest possible concentration (preferably greater than 1 g/cc)
- b coating the viscous solution obtained in the preceding step, which is a powder-bonding agent compound (B), on a device of the collector type, preferably on a collector of the metallic type and/or of the perforated metal collector type, said collector thus treated making up an electrode; and
- step b drying the electrode prepared in step b); the drying preferably being carried out using an infrared lamp or using a heating element.
- step c) two distinct means are used in parallel to dry the electrode, these means preferably being drying by infrared lamp and drying by heating element.
- a tap density measured according to the previously defined method preferably between 0.3 and 1.5, more preferably between 0.5 and 1.4, and most preferably between 1 and 1.3 g/cc;
- a granulometric dispersion measured according to the previously defined method such that the D90/D10 ratio varies between 2 and 5 and the particles have a size between 1 and 50 ⁇ m, preferably such that the D90/D10 ratio varies between 2.2 and 4.2 and the particles have a size between 2 and 30 ⁇ m.
- the size of these graphite-based particles is between 1 and 50 ⁇ m.
- these particles have a sphericity of 80% or more.
- a preferred sub-family is made up of particles in which the average thickness of the metallic and/or carbonated coating is between 50 nm and 2 ⁇ m.
- Another preferred sub-family is made up of graphite-based particles made up of a coated graphite core, said core making up at least 90% by weight of the total mass of the graphite-based particle, the remaining 10% preferably being made up of at least one metal selected from the group comprising Ag, Si, Al and Cu and/or carbon and/or a carbonated polymer, preferably in prismatic or fiber form.
- a tenth object of ‘the present ’ invention comprises a process for preparing the graphite-based particles using prismatic-shaped particles, by coating the particles while keeping the basal function (fb) and the edge function (fe) constant while wrapping the graphite surface with a metallic or carbonic deposit in such a way as to obtain a sphericity of 80% or more.
- An eleventh object of the present invention comprises a (preferably) in situ process for purifying the surface of graphite particles, by coating these particles, in the presence of their impurities, with carbon.
- a twelfth object of the present invention comprises the use of modified graphite particles according to the invention in an electrochemical cell, with a control of the basal function (fb) that permits their use in the presence of an electrolyte based on polyethylene carbonate (PC), the concentration of PC in the electrolyte then being less than 50% by volume of the electrolytic mixture.
- fb basal function
- PC polyethylene carbonate
- a thirteenth object of the present invention is made up of the use of the graphite-based particles according to the invention with a constant basal function (fb) which makes possible their use in the presence of an electrolyte based on polyethylene carbonate (PC), up to a PC concentration in the electrolyte that is then less than or equal to 100% by volume of the electrolytic mixture.
- the batteries resulting from this utilisation are safe and make up an object of the present invention.
- the grinding is stopped and an evaluation of the granulometry and of the specific surface area is carried out on the sample. If the desired granulometric distribution is not achieved, the grinding is repeated for a period of 10 minutes. These steps will be continued until a d 50 of 10 ⁇ m is obtained.
- a second 500 g sample is ground in an Alpine jet air grinder to obtain a d 50 of 10 ⁇ m.
- a comparative study using scanning microscopy is carried out on the two samples after grinding. This allows us to identify whether the shape of the flakes obtained by attrition comes closer to that of a sphere.
- the coating is more uniform
- Natural graphite made into spherical form combines the advantages of the two carbons: those of natural graphite and those of spherical artificial graphite.
- the energy is maintained at its maximum with natural graphite (average capacity and voltage).
- the contribution of the basal planes is reduced, which promotes on the one hand the reduction in irreversible capacity due to passivation and the increase of diffusional parts (edges) along the crystallographic axis C (perpendicular to the planes formed by the carbon atoms).
- the problem of anisotropy is reduced and the intercalation kinetic is improved.
- Spherical particles make coating of the electrodes more homogeneous and make the electrodes obtained less porous.
- the thickness of the electrodes with spherical particles is better controlled and can achieve smaller thicknesses for power applications, such as pulses for telecommunication and power take-offs for hybrid vehicles. These characteristics facilitate the design of super-thin Li-ion batteries up to the level of polymer batteries.
- a mathematical model for the spherical particle has been developed in order to express the relationship between the size of the graphite crystallite and the sites on the surface by using crystallographic parameters a, b and c.
- the sphere is formed of prismatic layers with dimension Ai.Bi (basal plane) and thickness T (edge) stacked on each other.
- parameters A and B are smaller by the same factor (Y) as they move away from the central layer (0) toward peak (n) or toward base (n) of the particle (FIG. 1).
- a 1 A/Y
- B 1 B/Y
- B 2 B 1 /Y B/Y 2
- B 3 B 2 /Y B/Y 3
- equation (6) Considering the symmetry of the sphere, equation (6) will take the form:
- B ⁇ ⁇ A ⁇ 2 ⁇ A ⁇ A ⁇ ⁇ B ⁇ [ 1 - 1 / Y 2 ⁇ n ] ⁇ ( 9 )
- equation (12) expresses the relationship between the surface of the edges as a function of the dimensions of the particle and of parameter Y.
- edge and basal surfaces are defined by:
- Y 1.001 B ( ⁇ ) T ( ⁇ ) Particle basal edge f e f e Gap (%) size ( ⁇ ) length length prismatic cylindrical (f e p ⁇ f e c) 2 2 0.21 0.99763 0.99526 0.2363 12 12 0.49 0.99392 0.98791 0.60089 20 20 1.54 0.99677 0.99355 0.32139 30 30 2.03 0.99632 0.99267 0.36523 40 40 2.85 0.99651 0.99303 0.34706
- the gap between the two, approximations increases with Y, as well as the effect of the particle size.
- the particles with small size are the easiest to make spherical (fe(2im)>fe(40im))
- Natural graphite is used that has an initial particle size of 375 ⁇ m, a purity rate 98% and in the shape of flakes.
- the specific surface area of this graphite is about 1 m 2 /g.
- the natural graphite powder is ground using an “attrition” process in order to transform these particles into spherical particles.
- the d 002 has not changed after a change to spherical shape and has a value of 3.36 angstroms.
- Analysis using scanning electron microscopy (SEM) has shown, in micrograph 1 a (FIG. 8/ 15 ) compared to micrograph 1 b (FIG. 9/ 15 ) before attrition, the change in the shape of the particles while the size is essentially maintained at the same scale.
- the fluorinated polyvinylidene PVDF bonding agent is solubilized in NMP N-methylpyrrolidone.
- An 80:20 mixture of the solvents acetone/toluene is added to the PVDF-NMP paste to form the coating composition.
- the natural graphite powder transformed into spheres is dispersed in the coating composition in a weight ratio of 90:10. This mixture is applied on a copper collector using the doctor blade method.
- the electrode is dried using an infrared lamp.
- the electrode is mounted in a 2035 button-type battery.
- a CelgardTM 2300 separator soaked with electrolyte 1M LiPF 6 +EC/DMC: 50:50 (ethylene carbonate+dimethyl carbonate) is used.
- Electrochemical tests were carried out at ambient temperature. The charge curves were obtained between 0 and 2.5 volts in C/24 for two button cells, P1 and P2 (FIG. 4), FIG. 10/ 15 . The reversible capacity is 370 mAh/g. This result is comparable to that obtained with electrodes prepared using standard natural graphite in flake form, as well as artificial graphite in spherical form (MCMB28-25).
- Natural graphite comprising particles with initial size of 375 ⁇ m, purity rate 98% and in the shape of flakes.
- the specific surface area of this graphite is around 1 m 2 /g.
- the particles are reduced to 20 ⁇ m by jet milling.
- the particles are cut to 10 ⁇ m in spherical shape by attrition.
- the jar mill method was used with ceramic balls having a diameter of 50 mm, for 24 hours. This mixture is ground by jet milling, the air pressure in the jet mill fluctuating between 100 and 125 psi during processing.
- the average size of the particles is reduced to between 10 and 20 ⁇ m and the particles obtained have the shape of a potato.
- FIG. 12/ 15 which is a scanning electron microscope micrograph, clearly shows the potato shapelike with a 12 ⁇ m particle.
- FIG. 13/ 15 which is a scanning electron microscope micrograph, clearly shows that the basal function (fb) decreases and the edge function (fe) increases, thus the graphite planes at the basal level join the graphite planes at the level of the edge in the form of a saw tooth (verification of mathematical model 1).
- This mixture is ground by jet milling.
- the dwell time of the mixture in the chamber is 45 minutes.
- air pressure in the jet mill fluctuates between 100 and 125 psi.
- the size of the particles is reduced to between 10 and 20 ⁇ m and the shape of the particles obtained is potatolike.
- FIG. 14/ 15 clearly shows the potatolike shape obtained with a 12 ⁇ m particle.
- a mixture is prepared of 2 g of Brazilian graphite with an average particle size (d 50 ) of 20 ⁇ m and prismatic shape, and 10% cellulose acetate.
- the mixture is dissolved in acetone and homogenized using the ball mill method.
- the mixture is processed at 400° C. for 3 hours in a nitrogen atmosphere.
- the particles obtained are potatolike shaped.
- the mixture is dissolved in acetone, then it is homogenized by ball milling. The mixture is processed at 400° C. for 3 hours in a nitrogen atmosphere.
- the particles obtained are potatolike shaped.
- One of the advantages of this treatment is that the carbonated layer obtained on the surface plays the role of a purifier since it covers all the impurities present at the surface.
- the deposit is obtained by evaporation, using an Edwards Coating System Model E306A evaporator.
- the reversible capacity is 387 mAh/g, 15 mA/g more than the theoretical capacity of natural graphite.
- a low specific surface area is associated with a lower passivation film contribution.
- this passivation layer forms on the basal part (organic species): ICL basal and on the edge part (inorganic species): ICL edge .
- ICL basal is 40 times higher than ICL edge . This shows that the decrease in the basal function is very important in order to reduce the the exhaut of gases. This is of the battery.
Abstract
The invention concerns modified graphite particles obtained from graphite or based on graphite, said particles having impurities in their internal structure and having, at the surface, a low, even nil, rate of an impurity or several impurities. Said particles further comprise at least one of the following characteristics: a tab density ranging between 0.3 and 1.5 g/cc; the shape of a potato; and a size distribution such that the D90/D10 ratio varies between 2 and 5 and the particles have a size ranging between 1 and 50 μm. Said particles are useful for fuel cells, electrochemical generators or moisture sensor and/or oxygen sensor and they have interesting electrochemical properties. The resulting electrochemical cells and batteries are stable and safe.
Description
- The present invention relates to modified graphite particles and to particles based on graphite that are also characterized in that they have a potatolike shape. The present invention also concerns processes that make it possible to prepare these new particles, as well as the use of the particles thus obtained in particular as moisture absorbers and/or oxygen absorbers. These processes can be monitored by controlling the values obtained from the mathematical functions that are characteristic of the shape of the crystalline (edge, basal, Lc and La) and geometric structures of the graphite. These new particles also exhibit, within the scope of an electrochemical application, improved stability to cycling by increasing, on one hand, the density of the electrode and on the other, the diffusion kinetics of the intercaling material (Li, Na or other).
- Graphite has important electrochemical properties. Thus for natural graphites, which are available abundantly in nature, a reversible capacity of 372 mAh/g and a voltage plateau close to that of lithium have been established.
- Graphite has been introduced into commercial lithium-ion batteries, as mentioned in the patent granted to Sanyo in the United States, under number U.S. Pat. No. 5,882,818. Its important characteristics, in addition to its low cost price, have made natural graphite a good candidate as anode in lithium-ion batteries. However, coating of uniform electrodes remains problematic due to the physical shape of these particles, which have the shape of flakes. For this reason, carrying out the coating effectively requires an additional calendering step when the electrodes for Li-ion batteries are manufactured (Energy Storage Systems for Electronics, by Testuya Osaka and Madhav Datta, (2000), page 125). The compactness density is low, which results in electrodes having greater thicknesses. The performances of the anode depend on the type of graphite and the physical shape of these particles. The efficiency of the first intercalation of the ion in graphite is dependent on the specific surface area and the edge surface fraction (K. Zaghib et al, J. Electrochemical Soc. 147 (6) 2110 to 2115, 2000). A low specific surface area is associated with a lower contribution of passivation film.
- Natural graphite is found exclusively in the form of flakes, while artificial graphite can be found in the form of flakes, fibers or spheres. The flake shape has an elevated degree of preferential orientation which will induce anisotropy in the electrode. An orientation such as this reduces the intercalation kinetics of lithium across the edges. However, the only spherical carbon available on the market is Mesocarbon Microbeads MCMB processed at 2,800° C. by Osaka Gas (T. Kasuh et al., J. Power Source 68 (1997), 99). This carbon is an artificial graphite that requires costly processing at high temperature to be ordered, as well as complex synthesis that can increase its production cost. The maximum reversible capacity obtained with this artificial graphite is of the order of 280 mAh/g, which is low in comparison to the corresponding capacity of natural graphite, which is 372 mAh/g.
- U.S. Pat. No. 6,139,990 of Kansai Netsukkagaku Kabushiki Kaisha granted on Oct. 31, 2000, describes graphite particles that are modified and rounded, having an almost spherical form, characterized in that their degree of circularity is greater than or equal to 0.86 and in that, using X-ray diffraction measurement, the peak of the intensity relationship between one face002 (parallel to the graphite layers) and face 110 (perpendicular to the graphite layers), that serve as the random orientation index, must not be less than 0.0050. These particles have poor homogeneity as regards their,granulometric distribution, which limits their use in electrochemical cells, especially with propylene carbonate as electrolyte. This represents a major disadvantage for low-temperature applications. A lack of safety of electrochemical cells incorporating such graphite particles is also noted.
- Patent application EP-A-0,916,618 filed in the name of the OSAKA GAS Co. Ltd., on the other hand, describes a graphite material in which the formation of cavities has been optimized in order to increase the electrochemical capacity of the electrodes containing it. While these materials have become interesting with regard to their use in primary-type batteries, they are of little interest for other electrochemical applications, in particular because of the fragility of their structure and the resulting lack of stability for capacities greater than 400 mA/g.
- The handling required for converting natural graphite into spherical graphite presents net advantages in comparison to the standard natural graphite present in the form of flakes, as well as in comparison to spherical artificial graphite (MCMB).
- Thus a need existed for graphite-based particles in a stable form that can be compressed easily to the point of obtaining an elevated density, these particles presenting electrochemical capacities and anisotropies that are greater than or equal to those of the known forms of graphite particles. In particular, these particles make it possible to produce homogeneous and compact electrodes and also promote the use of PC.
- The present invention especially concerns potatolike shaped modified graphite particles having impurities in their internal structure and having on the surface a low, even nil, rate of an impurity or several impurities, in particular the impurities usually present in natural graphites.
- The present invention also relates to particles based on modified graphite made up of prismatic graphite particles covered with a metallic deposit and/or a carbonic deposit.
- The graphite particles according to the present invention can be used, in particular, as humidity absorbers and/or oxygen absorbers and, especially because of their cycling performance, can be used in the manufacture of negative electrodes, preferably in the manufacture of negative electrodes for rechargeable electrochemical generators.
- The present invention also concerns methods that make possible the preparation of these particles and the preparation of electrodes containing them.
- FIG. 1/15: According to
model 1, transformation of the prismatic particles into spherical particles by decreasing the fb and increasing the fe. This transformation can be carried out using several techniques: jet mill, attrition, ball mill, hammer mill, CF mill or atomizer mill, planetary mixer, hybridizer. - According to
model 1, transformation of the prismatic particles into spherical particles by keeping fe and fb constant. This transformation is carried out by coating the particles with a metal, polymer or carbon. - FIG. 2/15: According to
model 2, transformation of the cylindrical particles into spherical particles by decreasing the fb and increasing the fe. This transformation can be carried out using several techniques: jet mill, attrition, ball mill, hammer mill, CF mill or atomizer mill, planetary mixer, hybridizer. - According to
model 2, transformation of the prismatic particles into spherical particles by keeping fe and fb constant. This transformation is carried out by coating the particles with a metal, polymer or carbon. - FIG. 3/15: According to
model 1, the prismatic-shaped artificial or natural graphite, in the presence of its impurities and, soluble agents of the NaCl and NH4F type or the like (preferably with spherical shape), is transformed into spherical-shaped graphite by decreasing the basal fraction (fb) and increasing the edge fraction (fe). This transformation can be carried out using several techniques: jet mill, attrition, ball mill, hammer mill, CF mill or atomizer mill, planetary mixer, hybridizer. - FIG. 4/15: According to
model 2, the carbon fiber, the cylindrical-shaped artificial or natural graphite, in the presence of its impurities and soluble agents of the NaCl and NH4F type or the like (preferably with spherical shape), is transformed into spherical-shaped graphite by decreasing the basal fraction (fb) and increasing the edge fraction (fe). This transformation can be carried out using several techniques: jet mill, attrition, ball mill, hammer mill, CF mill or atomizer mill, planetary mixer, hybridizer. - FIG. 5/15: According to
model 1, the prismatic-shaped artificial or natural graphite, in the presence of its impurities and non-soluble agents of the SiO2 and TiO2 type, ceramic, material, hard compound or the like (preferably with spherical shape) is transformed into spherical-shaped graphite by decreasing the basal fraction (fb) and increasing the edge fraction (fe). This transformation can be carried out using several techniques: jet mill, attrition, ball mill, hammer mill, CF mill or atomizer mill, planetary mixer, hybridizer. - FIG. 6/15: According to
model 2, the cylindrical-shaped artificial or natural graphite, in the presence of its impurities and non-soluble agents of the SiO2 and TiO2 type, ceramic material, hard compound or the like (preferably with spherical shape), is transformed into spherical-shaped graphite by decreasing the basal fraction (fb) and increasing the edge fraction (fe) This transformation can be carried out using several techniques: jet mill, attrition, ball mill, hammer mill, CF mill or atomizer mill, planetary mixer, hybridizer. - FIG. 7/15: Comparative modeling between the prismatic and cylindrical model for two types of particles of 2 and 40 μm.
- FIG. 8/15: Graphite particles before attrition.
- FIG. 9/15: Graphite particles after attrition.
- FIG. 10/15: Electrochemical results of natural graphite NG20, after attrition.
- FIG. 11/15: Electrochemical results with commercial spherical graphite MCMB.
- FIG. 12/15: Scanning electron microscope micrograph showing the potatolike shape of a 12 μm particle obtained in example 3, according to the invention.
- FIG. 13/15: Scanning electron microscope (MEB) micrograph showing the trend in basal and edge. functions for a graphite particle conforming to
mathematical model 1. - FIG. 14/15: Scanning electron microscope micrograph showing the potato shape of a 12 im graphite particle obtained in example 3.
- FIG. 15/15: Micrograph of a particle obtained in example 3, micrographed with the scanning electron microscope (MEB), showing that the basal function (fb) decreases and the function (fe) increases.
- A first object of the present invention comprises modified graphite particles obtained from graphite (preferably from synthetic graphite), the structural parameters of said particles corresponding to at least one of the equations
- fe1 =[Y+1]/[(Y+1)+(B/2T)(Y−1)] and fe2=[Y+1] [(Y+1)+(B/T) (Y−1)], where Y represents a whole number greater than or equal to 1, B represents the length of the particle in μm, T represents the thickness of the particle in μm. These particles also have a potatolike shape and have at least one of the following two characteristics:
- a tap density, measured according to the method associated with the instrument sold under the name of Logan Instrument Corp. Model Tap-2, between 0.3 and 1.5, preferably between 0.5 and 1.4, most preferably between 1 and 1.3 g/cc; and
- a granulometric dispersion measured according to the method associated with the particle analyzer sold under the name Microtac Model X100 Particle Analyzer, such that the D90/D10 distribution ratio varies between 2 and 5 and the particles have a size between 1 μm and 50 μm, preferably such that the D90/D10 distribution ratio varies between 2.2 and 4.2 and the particles have a size between 2 μm and 30 μm.
- A second object of the present invention comprises modified graphite particles obtained from graphite, said particles having a potatolike shape, comprising impurities in their internal structure and having on the surface a rate of one or more impurities, measured according to the retrodiffused detector method defined in the publication Kimoto S. and Hashimoto H., (1966), in Electron Microphone, John Wiley, New York, page 480 and in Gedcke, D. A., Ayers, J. B. and DeNee, P. B. (1978),SEM/1978, SEM Inc, AMF O'Hare, Ill., page 581, that is less than 10%, which preferably varies between 2% and 4%, and said particles also having at least one of the following three characteristics:
- a tap density measured according to the previously identified method between 0.3 and 1.5, preferably between 0.5 and 1.4, most preferably between 1 and 1.3 g/cc;
- a granulometric dispersion measured according to the previously identified method, such that the D90/D10 ratio varies between 2.2 and 4.2 and the particles have a size between 2 and 30 μm; and
- they have, attached to their surface, particles (preferably potatolike shape, most preferably spherical) of NaCl and/or NH4F; preferably the mass of these particles of NaCl and/or of NH4F represents 1 to 4% of the total mass of the modified graphite particles.
- The rate of impurities on the surface of graphite may be reduced in different ways; one particularly effective method is the one described in the application PCT/CA100233 held by the Hydro-Quebec Company. The contents of this document are incorporated in the present application by reference.
- A preferred sub-family of the particles according to the second object of the present application is made up of modified graphite particles for which TGA analysis carried out according to the method associated with the device sold under the name TGA/DTA Model SDT 2960, TA Instruments Inc., New Castle, Del., gives an initial temperature value between 560 and 660 degrees Celsius, associated with the loss of weight, as is illustrated in FIG. 11/11.
- The particle parts of graphite modified according to the invention may contain impurities, for example, at least one impurity from the group made up of the chemical elements Fe, Mo, Sb, As, V, Cr, Cu, Ni, Pb, Co, Ca, Al, Ge, Si, Ba, Be, Cd, Ce, Co, Ciu, Dy, Eu, La, Li, Mo, Nd, Ni, Pb and Pr.
- One preferred sub-family among the graphite particles according to the invention is made up of particles in which the percentage of impurities by weight present in the said particles, expressed with respect to the total mass of modified graphite particles and measured according to the ash method, is between 1 and 10%, and preferably between 2 and 4%.
- More especially interesting are the graphite particles according to the invention that are substantially lacking in surface impurities and preferably those devoid of surface impurities.
- A third object of the present invention comprises modified graphite particles obtained from graphite, said particles having a potatolike shape and containing from 5 to 20% of at least one of the following compounds SiO2, MgO, ceramic compounds or a mixture of these, said compounds preferably being attached to the modified graphite particles by physical forces and having at least one of the following three characteristics:
- a tap density measured according to the previously described method between 0.3 and 1.5, preferably between 0.4 and 1.4, most preferably between 1 and 1.3 g/cc;
- a granulometric dispersion measured according to the previously defined method, such that the D90/D10 ratio varies between 2 and 5 for particles with a size between 1 and 50 μm, preferably such that the D90/D10 ratio varies between 2.2 and 4.2 for particles having a size between 2 and 30 μm; and
- they have, attached to their surface, particles (preferably potatolike shaped, most preferably spherical) of NaCl and/or of NH4F; preferably the mass of these particles of NaCl and/or of NH4F represents 1 to 10% of the total weight of the modified graphite particles.
- One particularly advantageous family of graphite particles according to the present invention is made up of all the modified graphite particles in which the interplane distance d002 (measured according to the method associated with the diffractometer sold under the name XRD Analysis Siemens Model D500 Diffractometer) varies from 33 to 3.4 angstroms and/or the BET (measured using the method associated with the device Quantachrome Autosorb automated gas adsorption system using N2) varies between 0.5 g/m2 and 50 g/m2.
- Among the modified graphite particles of the invention, those having a cycling stability greater than 500 cycles are of particular interest in the scope of electrochemical applications.
- A fourth object of the present invention comprises a process for preparing graphite particles (preferably from natural graphite) that are the object of the present invention by using at least one physical means that makes possible the reduction of at least 50% of the basal function (fb) and the increase of at least 50% of the edge function (fe) of the graphite particles, such physical means preferably being attrition, a jet mill, ball mill, hammer mill, atomizer mill, in the presence of at least one chemical compound selected from the group made up of compounds of the formula MFz, in which M represents an alkaline or alkaline-earth metal and z represents 1 or 2 (preferably MFz represents CaF2, BaF2, LiF), NaC1 and NH4F or a mixture thereof, said compound or compounds preferably being added in solid form, preferably at the beginning of the step using the physical means that makes it possible to reduce the basal function defined by the equation fb=1−fe and to increase the function fe defined by the ratio (2B/La+T/doo2): (2B/d100+T:d002) in which B, La=d100(2n+1) represents d002, n represents a number of planes. These functions are defined and analyzed in detail in the publication Effect of Graphite Particle Size on Irreversible Capacity Loss, K. Zaghib, G. Nadeau, and K. Kinoshita, Journal of the Electrochemical Society 147 (6) 2110-2115 (2000). This document is incorporated into the present application in its entirety by reference.
- As described in application PCT/CA0100233 of Hydro-Quebec, the use of NH4F on the surface the graphite at the time of grinding is very important since NH4F, at the time of the purification of graphite in the presence of H2SO4 and H2O, generates HF to dissolve the impurities, in particular SiO2.
- In the same way., the use of NaCl on the surface of graphite at the time of grinding is very important, since, at the time of the purification of graphite in the presence of H2SO4, NaCl generates HCl which also dissolves the impurities on its surface, in particular the metals Fe, Mo and the like.
- According to an advantageous mode of using the method, the reduction of the basal function and the increase of the edge function, preferably the rounding of the particles, is carried out using a means of attrition, said means preferably being made up of balls such as steel balls, ceramic balls or a mixture of steel and ceramic balls.
- A fifth object of the present invention comprises a process for preparing modified graphite particles according to
claim - i) modification of the shape of the graphite particles by using at least one physical means making possible the reduction of at least 50% of the basal function (fb) and the increase of at least 50% of the edge function (fe) of synthetic graphite particles (preferably of natural graphite), such physical means preferably being attrition (preferably a jet mill, ball mill, hammer mill, an atomizer mill) in the presence of at least one chemical compound selected from the group consisting of compounds of the formula MFz, in which M represents an alkaline or alkaline-earth metal and z represents 1 or 2, MFz preferably represents CaF2, BaF2, LiF or a mixture thereof, the compound or compounds preferably being added in solid form, preferably at ambient temperature, preferably at the beginning of the step using the means that make possible the reduction of the basal function and the increase of the edge function; and
- ii) reduction in the amount of surface impurities, preferably by purification, preferably by chemical purification of the graphite particles obtained in step i).
- According to an advantageous embodiment, the graphite particles used at the beginning of the process have a size between 1 and 450 μm, preferably between 2 and 350 μm.
- According to another advantageous embodiment, the attrition process is carried out in the presence of an additive, preferably an additive of the metallic oxide type such as SiO2, TiO2, ZrO2, and preferably in the presence of steel balls, ceramic balls or in the presence of a mixture of steel and ceramic balls.
- A preferred variation comprises using the method according to the invention under conditions such that at least one of the two steps is carried out in a controlled atmosphere or in air, the controlled atmosphere preferably being based on nitrogen, argon, helium or a mixture of these gases.
- Step i) can be a hybrid step using both jet milling and attrition, the attrition preferably being carried out after jet milling is used.
- According to a particularly advantageous method, step i) of the method is carried out using jet milling.
- A sixth object of the present invention comprises modified graphite particles such as defined above and below, as moisture sensors and/or oxygen absorbers.
- A seventh object of the present invention comprises negative electrodes, preferably negative electrodes for a rechargeable electrochemical generator prepared with a bonding agent, preferably a bonding agent of the PVDF or PTFE type, and with graphite particles according to any one of the objects of the present invention.
- An eighth object of the present invention is made up of a process for preparing an electrode for a rechargeable generator based on graphite particles according to the present invention or based on graphite particles such as those obtained by a method according to the invention, comprising at least the following steps:
- a—solubilization of at least one bonding agent (preferably selected from the group comprising PVDF, PTFE) in a solvent (preferably in a strong solvent selected from the group comprising NMP (N-methylpyrrolidone), cyclopentanone at the highest possible concentration (preferably greater than 1 g/cc)) to obtain a viscous solution (A);
- b—coating the viscous solution obtained in the preceding step, which is a powder-bonding agent compound (B), on a device of the collector type, preferably on a collector of the metallic type and/or of the perforated metal collector type, said collector thus treated making up an electrode; and
- c—drying the electrode prepared in step b); the drying preferably being carried out using an infrared lamp or using a heating element.
- According to a preferred embodiment of this method, in step c) two distinct means are used in parallel to dry the electrode, these means preferably being drying by infrared lamp and drying by heating element.
- A ninth object of the present invention is made up of modified graphite-based particles that are made up of prismatic particles of graphite covered with a metallic deposit and/or a carbonic deposit, the structural parameters of said particles corresponding to the equations fe1=[Y+1]/[(Y+1)+(B/2T) (Y-1)] and fe2=[Y+1]/[(Y+1)+(B/T) (Y−1)], in which: Y represents a whole number greater than or equal to 1, B represents the length of the particle in μm, T represents the thickness of the particle in μm, said particles having a potatolike shape and having at least one of the following two characteristics:
- a tap density measured according to the previously defined method, preferably between 0.3 and 1.5, more preferably between 0.5 and 1.4, and most preferably between 1 and 1.3 g/cc; and
- a granulometric dispersion measured according to the previously defined method, such that the D90/D10 ratio varies between 2 and 5 and the particles have a size between 1 and 50 μm, preferably such that the D90/D10 ratio varies between 2.2 and 4.2 and the particles have a size between 2 and 30 μm.
- Preferably the size of these graphite-based particles is between 1 and 50 μm.
- According to an advantageous embodiment, these particles have a sphericity of 80% or more.
- Among all of these graphite-based particles, a preferred sub-family is made up of particles in which the average thickness of the metallic and/or carbonated coating is between 50 nm and 2 μm.
- Another preferred sub-family is made up of graphite-based particles made up of a coated graphite core, said core making up at least 90% by weight of the total mass of the graphite-based particle, the remaining 10% preferably being made up of at least one metal selected from the group comprising Ag, Si, Al and Cu and/or carbon and/or a carbonated polymer, preferably in prismatic or fiber form.
- A tenth object of ‘the present ’ invention comprises a process for preparing the graphite-based particles using prismatic-shaped particles, by coating the particles while keeping the basal function (fb) and the edge function (fe) constant while wrapping the graphite surface with a metallic or carbonic deposit in such a way as to obtain a sphericity of 80% or more.
- An eleventh object of the present invention comprises a (preferably) in situ process for purifying the surface of graphite particles, by coating these particles, in the presence of their impurities, with carbon.
- A twelfth object of the present invention comprises the use of modified graphite particles according to the invention in an electrochemical cell, with a control of the basal function (fb) that permits their use in the presence of an electrolyte based on polyethylene carbonate (PC), the concentration of PC in the electrolyte then being less than 50% by volume of the electrolytic mixture.
- The safety batteries resulting from this utilisation also make up an object of the present invention.
- A thirteenth object of the present invention is made up of the use of the graphite-based particles according to the invention with a constant basal function (fb) which makes possible their use in the presence of an electrolyte based on polyethylene carbonate (PC), up to a PC concentration in the electrolyte that is then less than or equal to 100% by volume of the electrolytic mixture. The batteries resulting from this utilisation are safe and make up an object of the present invention.
- Thus within the scope of the present invention, in particular, a new method for transforming the natural graphite particles into spherical particles is described. The coarse graphite powder, in the presence of these impurities that play a microabrasive role (HQ patent), having initial particles of 375 μm, is subject to grinding by attrition in order to reduce its size to a d50 of 10 μm. Steel balls are added to the graphite powder in a weight ratio of 1:10 graphite: balls. Grinding (ATTRITOR, type B, size S Union Process Inc, AKRON) is accelerated to a speed of 400 rpm for 60 minutes. After 60 minutes, the grinding is stopped and an evaluation of the granulometry and of the specific surface area is carried out on the sample. If the desired granulometric distribution is not achieved, the grinding is repeated for a period of 10 minutes. These steps will be continued until a d50 of 10 μm is obtained. A second 500 g sample is ground in an Alpine jet air grinder to obtain a d50 of 10 μm. A comparative study using scanning microscopy is carried out on the two samples after grinding. This allows us to identify whether the shape of the flakes obtained by attrition comes closer to that of a sphere. We have also used hybrid grinding; the size of the particle is reduced first to 20 μm by jet milling, then the particle is sized to 10 μm using attrition.
- The use of spherical graphite as anode in a rechargeable battery configuration has many advantages in comparison to graphite in flakes, in particular:
- the density of the consistency is increased;
- the coating is more uniform;
- the porosity is reduced;
- the fraction of basal planes is reduced;
- better inter-particle electrical contact;
- decomposition of the electrolyte is reduced;
- a rapid charge-discharge rate;
- the intercalation kinetics are better; and
- the safety of the battery is improved.
- Application of this process to natural graphite improves its electrochemical performance and its use for coating the electrode. Natural graphite made into spherical form combines the advantages of the two carbons: those of natural graphite and those of spherical artificial graphite. The energy is maintained at its maximum with natural graphite (average capacity and voltage). The contribution of the basal planes is reduced, which promotes on the one hand the reduction in irreversible capacity due to passivation and the increase of diffusional parts (edges) along the crystallographic axis C (perpendicular to the planes formed by the carbon atoms). In addition, the problem of anisotropy is reduced and the intercalation kinetic is improved. Spherical particles make coating of the electrodes more homogeneous and make the electrodes obtained less porous. The thickness of the electrodes with spherical particles is better controlled and can achieve smaller thicknesses for power applications, such as pulses for telecommunication and power take-offs for hybrid vehicles. These characteristics facilitate the design of super-thin Li-ion batteries up to the level of polymer batteries.
- Calculation models of the relationship between the graphite particles and their surfaces (basal and edge): comparison between the prismatic and spherical structure.
- Model I
- A mathematical model for the spherical particle has been developed in order to express the relationship between the size of the graphite crystallite and the sites on the surface by using crystallographic parameters a, b and c. In this model, it is assumed that the sphere is formed of prismatic layers with dimension Ai.Bi (basal plane) and thickness T (edge) stacked on each other.
-
- Central layer (0): A, B, T
- Layer (1):
- A l ,B 1 ,T where A=Y A 1 , B=Y B 1 and Y>1 (1)
- A 1 =A/Y, B 1 =B/Y
- Layer (2):
- A 2 ,B 2 Y where A 1 =YA 2 , B 1 =Y B 2 (2)
- A 2 =A 1 /Y=A/Y 2 , B 2 B 1 /Y=B/Y 2
- Layer (3):
- A 3 ,B 3 T where A 2 =YA 3 , B 2 =YB 3 (3)
- A 3 =A 2 /Y=A/Y 3 , B 3 B 2 /Y=B/Y 3
- Layer (n):
- A n , B n ,T where A n−1 =Y A n , B n−1 =YB n (4)
- A n =A n−1 /Y=A/Y n , B n =Bn 1−1 /Y=B/Y n
- Thus, for the surface of the edge:
- EA=2T[(A+B)+(A 1 +B d)+(A 2 +B 2)+(A 3 +B 3)+ . . . +(A n +B n)] (5)
-
- Considering the symmetry of the sphere, equation (6) will take the form:
- EA=4T(A+B)[Σ1/Y 1]−2T(A+B), (i=0 to n) (7)
- The series [Σ1/Y1] (i=0 to n) converges toward the term Y/(Y-1)
- (mathematic table 1+x+x2 +. . . +xn+=1/(1−x), where 1<x<1)
- EA=4T(A+B)Y(Y−1)−1−2T(A+B)
- EA=2T(A+B)[2Y(Y−1)−1−1] (8)
-
-
-
- f e =[Y+1]/[(Y+1)+[AB/T(A+B)[1−(1/Y 2n)](Y−1)] (10)
- When A=B;
- f e =[Y+1]/[(Y+1)+(B/2T)(1−Y− 2n)(Y−1)] (11)
- 1) in an ideal case, when n→∞, Y−2n→0; (when an infinite number of prismatic layers is considered)
- f e =[Y+1]/[(Y+1)+(B/2T)(Y−1)] (12)
- equation (12) expresses the relationship between the surface of the edges as a function of the dimensions of the particle and of parameter Y.
-
Model 2 -
- The edge and basal surfaces are defined by:
- EA=nBT
- BA=n B2/2
- hence fraction fe
- f e =[Y+1]/[(Y+1)+(B/T) (1−Y −2n)(Y−1)] (13)
- 1) When n→∞, Y−2n→0
- f e =[Y+1]/[(Y+1)+(B/T)(Y−1)] (14)
- In these two models, it is possible to see that the trend in the basal and edge planes of the prismatic shape toward the spherical shape causes a noticeable decrease of the surface area of the basal planes. This increases the edge surface fraction in comparison to the total surface area of the particle. From the electrochemical point of view, passivation will be reduced with the reduction of the basal surface and on the other hand, intercalation will be more accessible over a large edge surface. For a given value of parameter (Y), where Y≧1, it is possible to compare the fraction of the edgesurface fe obtained in equations 12 and 14. Tables 1.a-d present the results obtained for the edge fraction (fe) calculated for the two approximations.
TABLE 1a Y = 1.001 B (μ) T (μ) Particle basal edge fe fe Gap (%) size (μ) length length prismatic cylindrical (fep − fec) 2 2 0.21 0.99763 0.99526 0.2363 12 12 0.49 0.99392 0.98791 0.60089 20 20 1.54 0.99677 0.99355 0.32139 30 30 2.03 0.99632 0.99267 0.36523 40 40 2.85 0.99651 0.99303 0.34706 -
TABLE 2b Y = 1.01 B (μ) T (μ) Particle basal edge fe fe Gap (%) size (μ) length length prismatic cylindrical (fep − fec) 2 2 0.21 0.97686 0.95476 2.2096 12 12 0.49 0.94258 0.89139 5.1185 20 20 1.54 0.96871 0.93931 2.9396 30 30 2.03 0.96454 0.93151 3.303 40 40 2.85 0.96626 0.93473 3.1533 -
TABLE 3c Y = 1.1 B (μ) T (μ) Particle basal edge fe fe Gap (%) size (μ) length length prismatic cylindrical (fep − fec) 2 2 0.21 0.81516 0.68799 12.717 12 12 0.49 0.63168 0.46164 17.003 20 20 1.54 0.76382 0.61788 14.593 30 30 2.03 0.73972 0.58695 15.277 40 40 2.85 0.74953 0.5994 15.013 -
TABLE 4d Y = 1.5 B (μ) T (μ) Particle basal edge fe fe Gap (%) size (μ) length length prismatic cylindrical (fep− fec) 2 2 0.21 0.5122 0.34426 16.793 12 12 0.49 0.28994 0.16955 12.039 20 20 1.54 0.43503 0.27798 15.705 30 30 2.03 0.40358 0.2528 15.078 40 40 2.85 0.41606 0.26267 15.339 - The best approximation is normally obtained with a value of parameter Y closest to the unit. For Y=1.001, the value of fe in the approximations converges toward one, independently of the size of the particles.
- This means that the surface of basal planes I tends toward zero, which is the ideal case (Table 1a).
- The gap between the two, approximations increases with Y, as well as the effect of the particle size. When Y=1.01, there is a 3% gap between the two approximations and less than 2% between the size of the particles. While at Y=1.5, the gap is around 16%, while that between the particles remains between 2-3%.
- This variation in factor fe depends on the way the shape of the elementary particles is considered, as well as the step between them (Y), which will form the final spherical particle. The divergence of fe from the unit gives the fraction of basal planes. In fact, the spherical form of the natural graphite particles is more advantageous and makes it possible to have a more rapid intercalation rate and less irreversible capacity (less basal surface).
- 2) When the term (1−Y−2n) is considered in equations (11) and (13);
- if Y=1.1, the two equations rapidly converge (FIG. 3) after n iterations (n<50). As shown in FIG. 7/15, the results obtained show that:
- the particles with small size are the easiest to make spherical (fe(2im)>fe(40im))
- a prismatic approximation gives higher values for fe.
- The following examples, which are given purely by way of illustration, should not be interpreted as constituting any limitation of the present invention.
- Natural graphite is used that has an initial particle size of 375 μm, a purity rate 98% and in the shape of flakes. The specific surface area of this graphite is about 1 m2/g. The natural graphite powder is ground using an “attrition” process in order to transform these particles into spherical particles.
- The d002 has not changed after a change to spherical shape and has a value of 3.36 angstroms. Analysis using scanning electron microscopy (SEM) has shown, in micrograph 1 a (FIG. 8/15) compared to micrograph 1 b (FIG. 9/15) before attrition, the change in the shape of the particles while the size is essentially maintained at the same scale.
- The fluorinated polyvinylidene PVDF bonding agent is solubilized in NMP N-methylpyrrolidone. An 80:20 mixture of the solvents acetone/toluene is added to the PVDF-NMP paste to form the coating composition. The natural graphite powder transformed into spheres is dispersed in the coating composition in a weight ratio of 90:10. This mixture is applied on a copper collector using the doctor blade method. The electrode is dried using an infrared lamp. The electrode is mounted in a 2035 button-type battery. A Celgard™ 2300 separator soaked with electrolyte 1M LiPF6+EC/DMC: 50:50 (ethylene carbonate+dimethyl carbonate) is used.
- Electrochemical tests were carried out at ambient temperature. The charge curves were obtained between 0 and 2.5 volts in C/24 for two button cells, P1 and P2 (FIG. 4), FIG. 10/15. The reversible capacity is 370 mAh/g. This result is comparable to that obtained with electrodes prepared using standard natural graphite in flake form, as well as artificial graphite in spherical form (MCMB28-25).
- Natural graphite is used comprising particles with initial size of 375 μm, purity rate 98% and in the shape of flakes. The specific surface area of this graphite is around 1 m2/g. In a first step, the particles are reduced to 20 μm by jet milling. In a second step, the particles are cut to 10 μm in spherical shape by attrition.
-
- To homogenize the mixture, the jar mill method was used with ceramic balls having a diameter of 50 mm, for 24 hours. This mixture is ground by jet milling, the air pressure in the jet mill fluctuating between 100 and 125 psi during processing.
- At the end of the processing, the average size of the particles is reduced to between 10 and 20 μm and the particles obtained have the shape of a potato.
- FIG. 12/15, which is a scanning electron microscope micrograph, clearly shows the potato shapelike with a 12 μm particle.
- FIG. 13/15, which is a scanning electron microscope micrograph, clearly shows that the basal function (fb) decreases and the edge function (fe) increases, thus the graphite planes at the basal level join the graphite planes at the level of the edge in the form of a saw tooth (verification of mathematical model 1).
- 20 kg of Brazilian graphite with an average particle size (d50) of 350 μm and a purity of 98.5% is mixed in a reactor with 10% by weight of NaCl.
- Homogenization of the mixture is carried out using the jar mill method with ceramic balls having a diameter of 50 mm, for 24 hours.
- This mixture is ground by jet milling. The dwell time of the mixture in the chamber is 45 minutes.
- During processing, air pressure in the jet mill fluctuates between 100 and 125 psi.
- In the course of processing, the size of the particles is reduced to between 10 and 20 μm and the shape of the particles obtained is potatolike.
- The scanning electron microscope micrograph (MEB), FIG. 14/15, clearly shows the potatolike shape obtained with a 12 μm particle.
- The scanning electron microscope micrograph (FIG. 15/15) clearly shows that the basal function (fb) decreases and that the edge function (fe) increases, a result of the rounding of the particle (verification of mathematical model 1).
- In a 200 ml container, a mixture is prepared of 2 g of Brazilian graphite with an average particle size (d50) of 20 μm and prismatic shape, and 10% cellulose acetate.
- The mixture is dissolved in acetone and homogenized using the ball mill method. The mixture is processed at 400° C. for 3 hours in a nitrogen atmosphere.
- The particles obtained are potatolike shaped.
- One of the advantages of this treatment is that the carbonated layer obtained on the surface plays the role of purifier since it covers all the impurities existing at the surface.
- In a 200 ml reactor, a mixture of 2 g of Brazilian graphite with an average particle size (d50) of 20 μm and prismatic shape, and 10% of the PE-PEO-glycol compound is prepared.
- The mixture is dissolved in acetone, then it is homogenized by ball milling. The mixture is processed at 400° C. for 3 hours in a nitrogen atmosphere.
- The particles obtained are potatolike shaped.
- One of the advantages of this treatment is that the carbonated layer obtained on the surface plays the role of a purifier since it covers all the impurities present at the surface.
- A Brazilian graphite with an average particle size (d50) of 20 μm and prismatic shape, with a purity of 98.5%, is covered on its surface with a 10% by weight silver deposit.
- The deposit is obtained by evaporation, using an Edwards Coating System Model E306A evaporator.
- The reversible capacity is 387 mAh/g, 15 mA/g more than the theoretical capacity of natural graphite.
- A low specific surface area is associated with a lower passivation film contribution. Within the scope of the present invention, it has thus been established that this passivation layer forms on the basal part (organic species): ICLbasal and on the edge part (inorganic species): ICLedge. In summary, ICLbasal is 40 times higher than ICLedge. This shows that the decrease in the basal function is very important in order to reduce the the exhaut of gases. This is of the battery.
Claims (34)
1. Modified graphite particles obtained from graphite (preferably from synthetic graphite), the structural parameters of the said particles corresponding to at least one of the equations fle=[Y+1]/[(Y+1)+(B/2T)(Y−1)] and f2e=[Y+1]/[(Y+1)+(B/T)(Y−1)], where Y represents a whole number greater than or equal to 1, B represents the length of the particle in μm, T represents the thickness of the particle in μm, said particles having a potatolike shape and having at least one of the following two characteristics:
a tab density between 0.3 and 1.5, preferably between 0.5 and 1.4, most preferably between 1 and 1.3 g/cc; and
a granulometric dispersion such that the D90/D10 distribution ratio varies between 2 and 5 and the particles have a size between 1 μm and 50 μm, preferably such that the D90/D10 distribution ratio varies between 2.2 and 4.2 and the particles have a size between 2 μm and 30 μm.
2. Modified graphite particles obtained from graphite, said particles having a potatolike shape, having impurities in their internal structure and having on their surface an amount of one or more impurities that preferably varies between 2% and 4%, and the said particles also having at least one of the following three characteristics:
a tab density measured according to the previously identified method between 0.3 and 1.5, preferably between 0.5 and 1.4, most preferably between 1 and 1.3 g/cc;
a granulometric dispersion measured according to the previously identified method, such that the D90/D10 ratio varies between 2.2 and 4.2 and the particles have a size between 2 and 30 μm; and
they have, attached to their surface, particles (preferably potatolike shaped, most preferably spherical) of NaCl and/or of NH4F; preferably the mass of these particles of NaCl and/or of NH4F represents 1 to 10%, preferably 1 to 4%, of the total mass of the modified graphite particles.
3. Modified graphite particles according to claim 2 , characterized in that TGA analysis values give an initial temperature value associated with the loss of weight between 560 and 660 degrees Celsius.
4. Modified graphite particles according to any one of claims 1 to 3 , in which the impurities present are at least one chemical element selected from the group comprising Fe, Mo, Sb, As, V, Cr, Cu, Ni, Pb, Co, Ca, Al, Ge, Si, Ba, Be, Cd, Ce, Co, Ciu, Dy, Eu, La, Li, Mo, Nd, Ni, Pb and Pr.
5. Modified graphite particles according to claim 4 , in which the percentage of impurities by weight present in the said particles, expressed with respect to the total weight of modified graphite particles and measured according to the ash method, is between 1 and 10%, and preferably between 2 and 4%.
6. Modified graphite particles according to claim 5 , substantially devoid of surface impurities, preferably devoid of surface impurities.
7. Modified graphite particles obtained from graphite, said particles having a potatolike shape and containing from 5 to 20% of at least one of the following compounds SiO2, MgO, ceramic compounds or a mixture thereof, said compounds preferably being attached to the modified graphite particles by physical forces and having at least one of the following three characteristics:
a tab density measured according to the previously described method between 0.3 and 1.5, preferably between 0.4 and 1.4, most preferably between 1 and 1.3 g/cc;
a granulometric dispersion measured according to the previously defined method, such that the D90/D10 ratio varies between −2 and 5 for a particle size between 1 and 50 μm, preferably such that the D90/D10 ratio varies between 2.2 and 4.2 for a particle size between 2 and 30 μm; and
they have, attached to their surface, particles (preferably of . . . shape) of NaCl and/or of NH4F; preferably the mass of these particles of NaCl and/or of NH4F represents 1 to 4% of the total weight of the modified graphite particles.
8. Modified graphite particles according to'any one of claims 1 to 7 , in which the interplane distance d002 varies from 33 to 3.4 angstroms and/or the BET varies between 0.5 g/m2 and 50 g/m2.
9. Modified graphite particles according to any one of claims 1 to 8 , having a cycling stability greater than 500 cycles.
10. Process for preparing graphite particles (preferably from natural graphite) according to any one of claims 6 to 9 , by using at least one physical means that permits a reduction of at least 50% of the basal function (fb) and an increase of at least 50% of the edge function (fe) of the graphite particles, such physical means preferably being attrition, a jet mill, ball mill, hammer mill, atomizer mill, in the presence of at least one chemical compound chosen from the group consisting of compounds of the formula MFz, in which M represents an alkaline or alkaline-earth metal and z represents 1 or 2 (preferably MFz represents CaF2, BaF2,LiF), NaC1 and NH4F or a mixture thereof, said compound or compounds preferably being added in solid form, preferably at the beginning of the step using the physical means that permit a reduction of the basal function.
11. Process according to claim 10 , in which the reduction of the basal function and the increase of the edge function, preferably the rounding of the particles is carried out preferably using a means of attrition, the said means preferably being made up of balls such as steel balls, ceramic balls or a mixture of steel and ceramic balls.
12. Process for preparing modified graphite particles according to claim 1 or 2, preferably from natural graphite, comprising at least the following two steps:
i) modification of the shape of the graphite particles by using at least one physical means permitting a reduction of at least 0.50% of the basal function (fb) and an increase of at least 50% of the edge function (fe) of synthetic graphite particles (preferably of natural graphite), such physical means preferably being attrition (preferably a jet mill, ball mill, hammer mill, an atomizer mill) in the presence of at least one chemical compound selected from the group comprising compounds of the formula MFz, in which M represents an alkaline or alkaline-earth metal and z represents 1 or 2, MFz preferably represents CaF2, BaF2, LiF or a mixture of these, the compound or compounds preferably being added in solid form, preferably at ambient temperature, preferably at the beginning of the step for use of the means that permit the reduction of the basal function and the increase of the edge function; and
ii) reduction in the amount of surface impurities, preferably by purification, preferably by chemical purification of the graphite particles obtained in the preceding step i).
13. Process according to any one of claims 10 to 12 , in which the graphite particles used at the beginning of the process have a size between 1 and 450 μm, preferably between 2 and 350 μm.
14. Process according to any one of claims 10 to 13 , in which the attrition process is carried out in the presence of an additive, preferably an additive of the metallic oxide type such as SiO2, TiO2, ZrO2, and preferably in the presence of steel balls, ceramic balls or in the presence of a mixture of steel and ceramic balls.
15. Process according to any one of claims 10 to 14 , in which at least one of the two steps is carried out in a controlled atmosphere or in air, the controlled atmosphere preferably being based on nitrogen, argon, helium or a mixture of these gases.
16. Process according to any one of claims 9 to 15 , in which step i) is a hybrid step using jet milling and attrition, the attrition preferably being carried out after jet milling is used.
17. Process according to any one of claims 10 to 15 , in which step i) is carried out using jet milling.
18. Use of the modified graphite particles according to any one of claims 1 to 9 for fuel cells, electrochemical generators, as moisture sensors and/or as oxygen sensors.
19. Negative electrode, preferably for a rechargeable electrochemical generator prepared with a bonding agent, preferably a bonding agent of the PVDF or PTFE type, and with graphite particles according to any one of claims 1 to 8 .
20. Process for preparing an electrode based on graphite particles as defined in any one of claims 1 to 9 or based on graphite particles such as those obtained by a process according to any one of claims 1 to 17 for a rechargeable generator comprising at least the following steps:
a—solubilization of at least one bonding agent (preferably selected from the group comprising PVDF, PTFE) in a solvent (preferably in a strong solvent selected from the group comprising NMP (N-methylpyrrolidone), cyclopentanone at the highest possible concentration (preferably greater than 1 g/cc)) to obtain a viscous solution (A);
b—coating the viscous solution obtained in the preceding step, which is a powder-bonding agent-composition mixture (B), on a device of the collector type, preferably on a collector of the metallic type and/or of the perforated metal collector type, said collector thus treated making up an electrode; and
c—drying the electrode prepared in step b the drying is preferably carried out using an infrared lamp or using a heating element.
21. Process for preparing an electrode based on graphite for a rechargeable generator according to claim 20 , the method comprising all the steps cited in claim 18 with the exception of step (c) where two means of drying the electrode are used in parallel, drying with an infrared lamp and a heating element.
22. Modified graphite-based particles made up of prismatic particles of graphite covered with a metallic deposit and/or a carbonic deposit, the structural parameters of the said particles corresponding to the equations fe1=[Y+l]/[(Y+1)+(B/2T)(Y−1)] and fe2=[Y+1]/(Y+1)+(B/T) (Y−1)], in which: Y represents a real number greater than or equal to 1, B represents the length of the particle, T represents the thickness of the particle, said particles having the a potatolike shape and having at least one of the following two characteristics:
a tab density measured according to the previously defined method, preferably between 0.3 and 1.5, more preferably between 0.5 and 1.4, and most preferably between 1 and 1.3 g/cc;
a granulometric dispersion measured according to the previously defined method, such that the D90/D10 ratio varies between 2 and 5 and the particles have a size between 1 and 50 μm, preferably such that the D90/D10 ratio varies between 2.2 and 4.2 and the particles have a size between 2 and 30 μm.
23. Graphite-based particles according to claim 22 having a size between 1 and 50 μm.
24. Graphite-based particles according to claim 22 or 23, having a sphericity of 80% or more.
25. Graphite-based particles according to any one of claims 22 to 24 , in which the average thickness of the metallic and/or carbonated coating is between 50 nm and 2 μm.
26. Graphite-based particles made up of a coated graphite core, said core making up at least 90% by weight of the total weight of the graphite-based particle, the remaining 10% preferably being made up of at least one metal selected from the group comprising Ag, Si, Al and Cu and/or of carbon and/or of carbonated polymer, preferably in prismatic or fiber form.
27. Process for preparing graphite-based particles according to any one of claims 22 to 26 , using prismatic-shaped particles, by coating the particles while keeping the basal function (fb) and the edge function (fe) constant while wrapping the graphite surface with a metallic or carbonic deposit in such a way as to obtain a sphericity of 80% or more.
28. Use of the modified graphite-based particles such as defined in any one of claims 22 to 26 or such as obtained by one of the processes defined in any one of claims 13 to 27 for fuel cells, electrochemical generators or as moisture absorbers and/or oxygen absorbers.
29. Negative electrode, preferably for a rechargeable electrochemical generator prepared with a bonding agent, preferably a bonding agent of the PVDF, PTFE type and with graphite particles as defined in any one of claims 22 to 26 or such as obtained by the process defined in claim 27 .
30. Process for in situ purification of the surface of graphite particles by coating the particles, in the presence of their impurities, with carbon.
31. Use in an electrochemical cell of the particles according to claim 1 , with a control of the basal function (fb) that permits their use in the presence of an electrolyte based on polyethylene carbonate (PC), the concentration of PC in the electrolyte then being less than 50% by volume of the electrolytic mixture.
32. Safe battery resulting from the use described in claim 31 .
33. Use of the graphite-based particles according to claim 22 , with a constant basal function (fb) which permits their use in the presence of an electrolyte based on polyethylene carbonate (PC), up to a concentration of PC in the electrolyte that is then less than 100% by volume of the electrolytic mixture.
34. Safe battery resulting from the use described in claim 33.
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US12/572,510 US9444092B2 (en) | 2000-10-25 | 2009-10-02 | Potato-shaped graphite particles with low impurity rate at the surface, method for preparing the same |
US13/617,084 US9312537B2 (en) | 2000-10-25 | 2012-09-14 | Potato-shaped graphite particles with low impurity rate at the surface, method for preparing the same |
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US14/878,742 US9412999B2 (en) | 2000-10-25 | 2015-10-08 | Potato-shaped graphite particles with low impurity rate at the surface, method for preparing the same |
US14/933,436 US9508983B2 (en) | 2000-10-25 | 2015-11-05 | Potatolike shaped graphite particles with low impurity rate at the surface, process for preparing same |
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CA002324431A CA2324431A1 (en) | 2000-10-25 | 2000-10-25 | New process for obtaining natural graphite particles in spherical shape: modelling and application |
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PCT/CA2001/001511 WO2002034670A1 (en) | 2000-10-25 | 2001-10-24 | Potato-shaped graphite particles with low impurity rate at the surface, method for preparing same |
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US12/572,510 Active 2024-11-28 US9444092B2 (en) | 2000-10-25 | 2009-10-02 | Potato-shaped graphite particles with low impurity rate at the surface, method for preparing the same |
US13/617,084 Expired - Lifetime US9312537B2 (en) | 2000-10-25 | 2012-09-14 | Potato-shaped graphite particles with low impurity rate at the surface, method for preparing the same |
US13/857,861 Expired - Fee Related US9184437B2 (en) | 2000-10-25 | 2013-04-05 | Potato-shaped graphite particles with low impurity rate at the surface, method for preparing the same |
US14/878,742 Expired - Lifetime US9412999B2 (en) | 2000-10-25 | 2015-10-08 | Potato-shaped graphite particles with low impurity rate at the surface, method for preparing the same |
US14/933,436 Expired - Lifetime US9508983B2 (en) | 2000-10-25 | 2015-11-05 | Potatolike shaped graphite particles with low impurity rate at the surface, process for preparing same |
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US20060062716A1 (en) * | 2002-03-01 | 2006-03-23 | Hydro-Quebec | Method for the surface purification of a graphite containing impurities using a dilute aqueous solution of nh4f and h2so4 |
US20070021547A1 (en) * | 2005-05-27 | 2007-01-25 | Hiroyuki Suzuki | Resin compositions with a low coefficient of thermal expansion and articles therefrom |
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Publication number | Priority date | Publication date | Assignee | Title |
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4054687A (en) * | 1976-06-01 | 1977-10-18 | United Technologies Corporation | Method for making a fuel cell electrode |
US4263376A (en) * | 1980-02-04 | 1981-04-21 | Institute Of Gas Technology | Fuel cell electrode |
US4270348A (en) * | 1979-07-23 | 1981-06-02 | General Motors Corporation | Materials and method for preventing high temperature seize between metal parts |
US4637197A (en) * | 1984-10-15 | 1987-01-20 | Epoxy Technology, Inc. | Method and compositions for removal of moisture |
US4867803A (en) * | 1985-03-25 | 1989-09-19 | Kabushiki Kaisha Toshiba | Lapping tools and method of manufacturing the same |
US5478364A (en) * | 1993-05-14 | 1995-12-26 | Sharp Kabushiki Kaisha | Method of manufacturing lithium secondary battery |
US5882818A (en) * | 1991-11-12 | 1999-03-16 | Sanyo Electric Co., Ltd. | Lithium secondary battery |
US6064908A (en) * | 1996-11-07 | 2000-05-16 | Elf Aquitaine | Device for ionophoresis comprising at least a membrane electrode assembly, for the transcutaneous administration of active principles to a subject |
US6139990A (en) * | 1998-03-18 | 2000-10-31 | Kansai Netsukagaku Kabushiki Kaisha | Modified graphite particles derived from scaly natural ones, production thereof and secondary battery |
US6403259B1 (en) * | 1997-05-30 | 2002-06-11 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery comprising carbon particles with a plural-layer structure |
US20050207966A1 (en) * | 2000-02-25 | 2005-09-22 | Karim Zaghib | Surface preparation of natural graphite and the effect of impurities on grinding and the particle distribution |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3440181A (en) | 1965-03-22 | 1969-04-22 | Dow Chemical Co | Metal coated vermicular expanded graphite and polymer composition containing same |
US4028274A (en) * | 1976-06-01 | 1977-06-07 | United Technologies Corporation | Support material for a noble metal catalyst and method for making the same |
US4240830A (en) * | 1978-11-30 | 1980-12-23 | Westinghouse Electric Corp. | Method for making sintered metal-coated graphite for high-current collector brushes |
US5045349A (en) * | 1989-08-16 | 1991-09-03 | The United States Of America As Represented By The Secretary Of The Navy | Silver-nickel composite cathodes for alkaline secondary batteries |
JPH05213611A (en) * | 1991-08-09 | 1993-08-24 | Asahi Glass Co Ltd | Treatment of graphitic powder and graphite powder for making them hydrophilic |
JP2976300B1 (en) * | 1995-11-14 | 1999-11-10 | 大阪瓦斯株式会社 | Method for producing negative electrode material for lithium secondary battery |
JP3481063B2 (en) * | 1995-12-25 | 2003-12-22 | シャープ株式会社 | Non-aqueous secondary battery |
JP3873325B2 (en) | 1996-07-25 | 2007-01-24 | 大阪瓦斯株式会社 | Carbon material for lithium secondary battery negative electrode and method for producing the same |
JP3193342B2 (en) * | 1997-05-30 | 2001-07-30 | 松下電器産業株式会社 | Non-aqueous electrolyte secondary battery |
JP4029947B2 (en) * | 1997-05-30 | 2008-01-09 | 三菱化学株式会社 | Method for producing highly filling carbonaceous powder |
JP3916012B2 (en) * | 1997-05-30 | 2007-05-16 | 三菱化学株式会社 | Non-aqueous secondary battery electrode |
JPH1131508A (en) * | 1997-07-09 | 1999-02-02 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
JPH11157816A (en) | 1997-11-21 | 1999-06-15 | Unitika Ltd | Spherical vitreous carbon covered with metal |
US6828064B1 (en) * | 1998-01-07 | 2004-12-07 | Eveready Battery Company, Inc. | Alkaline cell having a cathode incorporating enhanced graphite |
EP0977292A2 (en) * | 1998-07-31 | 2000-02-02 | Mitsui Mining Co., Ltd. | Anode material for lithium secondary battery, process for production thereof, and lithium secondary battery |
JP3106129B2 (en) * | 1998-07-31 | 2000-11-06 | 三井鉱山株式会社 | Anode material for lithium secondary battery, method for producing the same, and lithium secondary battery |
EP2219253B1 (en) | 1998-09-18 | 2015-06-10 | Canon Kabushiki Kaisha | Electrode material |
JP3620703B2 (en) | 1998-09-18 | 2005-02-16 | キヤノン株式会社 | Negative electrode material for secondary battery, electrode structure, secondary battery, and production method thereof |
JP3685364B2 (en) * | 1999-03-23 | 2005-08-17 | シャープ株式会社 | Method for producing carbon-coated graphite particles and non-aqueous secondary battery |
US6528033B1 (en) | 2000-01-18 | 2003-03-04 | Valence Technology, Inc. | Method of making lithium-containing materials |
CA2324431A1 (en) * | 2000-10-25 | 2002-04-25 | Hydro-Quebec | New process for obtaining natural graphite particles in spherical shape: modelling and application |
KR101047983B1 (en) | 2008-07-31 | 2011-07-13 | 한국과학기술연구원 | AAA laminated graphite and its manufacturing method |
-
2000
- 2000-10-25 CA CA002324431A patent/CA2324431A1/en not_active Abandoned
-
2001
- 2001-10-24 CA CA2422660A patent/CA2422660C/en not_active Expired - Lifetime
- 2001-10-24 US US10/381,843 patent/US20040053050A1/en not_active Abandoned
- 2001-10-24 AU AU2002213710A patent/AU2002213710A1/en not_active Abandoned
- 2001-10-24 EP EP01982009A patent/EP1334065B1/en not_active Expired - Lifetime
- 2001-10-24 JP JP2002537668A patent/JP4610851B2/en not_active Expired - Lifetime
- 2001-10-24 DE DE60108163T patent/DE60108163T2/en not_active Expired - Lifetime
- 2001-10-24 AT AT01982009T patent/ATE285989T1/en not_active IP Right Cessation
- 2001-10-24 WO PCT/CA2001/001511 patent/WO2002034670A1/en active IP Right Grant
-
2006
- 2006-11-30 US US11/606,231 patent/US20070071669A1/en not_active Abandoned
-
2009
- 2009-03-30 JP JP2009083796A patent/JP5740079B2/en not_active Expired - Lifetime
- 2009-10-02 US US12/572,510 patent/US9444092B2/en active Active
-
2012
- 2012-09-14 US US13/617,084 patent/US9312537B2/en not_active Expired - Lifetime
-
2013
- 2013-04-05 US US13/857,861 patent/US9184437B2/en not_active Expired - Fee Related
- 2013-07-29 JP JP2013156614A patent/JP2014028753A/en active Pending
-
2015
- 2015-10-08 US US14/878,742 patent/US9412999B2/en not_active Expired - Lifetime
- 2015-11-05 US US14/933,436 patent/US9508983B2/en not_active Expired - Lifetime
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4054687A (en) * | 1976-06-01 | 1977-10-18 | United Technologies Corporation | Method for making a fuel cell electrode |
US4270348A (en) * | 1979-07-23 | 1981-06-02 | General Motors Corporation | Materials and method for preventing high temperature seize between metal parts |
US4263376A (en) * | 1980-02-04 | 1981-04-21 | Institute Of Gas Technology | Fuel cell electrode |
US4637197A (en) * | 1984-10-15 | 1987-01-20 | Epoxy Technology, Inc. | Method and compositions for removal of moisture |
US4867803A (en) * | 1985-03-25 | 1989-09-19 | Kabushiki Kaisha Toshiba | Lapping tools and method of manufacturing the same |
US5882818A (en) * | 1991-11-12 | 1999-03-16 | Sanyo Electric Co., Ltd. | Lithium secondary battery |
US5478364A (en) * | 1993-05-14 | 1995-12-26 | Sharp Kabushiki Kaisha | Method of manufacturing lithium secondary battery |
US6064908A (en) * | 1996-11-07 | 2000-05-16 | Elf Aquitaine | Device for ionophoresis comprising at least a membrane electrode assembly, for the transcutaneous administration of active principles to a subject |
US6403259B1 (en) * | 1997-05-30 | 2002-06-11 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery comprising carbon particles with a plural-layer structure |
US6139990A (en) * | 1998-03-18 | 2000-10-31 | Kansai Netsukagaku Kabushiki Kaisha | Modified graphite particles derived from scaly natural ones, production thereof and secondary battery |
US20050207966A1 (en) * | 2000-02-25 | 2005-09-22 | Karim Zaghib | Surface preparation of natural graphite and the effect of impurities on grinding and the particle distribution |
Cited By (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040262584A1 (en) * | 2002-01-14 | 2004-12-30 | Anthony Bonnet | Microcomposite powder based on flat graphite particles and on a fluoropolymer and objects made from same |
US7494740B2 (en) | 2002-01-14 | 2009-02-24 | Commissariat A L'energie Atomique | Microcomposite powder based on flat graphite particles and on a fluoropolymer and objects made from same |
US20060062716A1 (en) * | 2002-03-01 | 2006-03-23 | Hydro-Quebec | Method for the surface purification of a graphite containing impurities using a dilute aqueous solution of nh4f and h2so4 |
US20080124516A1 (en) * | 2004-03-19 | 2008-05-29 | Ngk Insulators, Ltd. | Method for Producing Porous Ceramic Structure |
US20100029833A1 (en) * | 2005-05-27 | 2010-02-04 | E.I. Du Pont De Nemours And Company | Resin compositions with a low coefficient of thermal expansion and articles therefrom |
US20070021547A1 (en) * | 2005-05-27 | 2007-01-25 | Hiroyuki Suzuki | Resin compositions with a low coefficient of thermal expansion and articles therefrom |
US20070112243A1 (en) * | 2005-08-11 | 2007-05-17 | United States Of America As Represented By The Administrator Of The National Aeronautics And Spac | Bimetallic Treatment System and its Application for Removal and Remediation of Polychlorinated Biphenyls (PCBs) |
US8163972B2 (en) | 2005-08-11 | 2012-04-24 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Zero-valent metallic treatment system and its application for removal and remediation of polychlorinated biphenyls (PCBs) |
US20100217063A1 (en) * | 2005-08-11 | 2010-08-26 | Usa As Represented By The Administrator Of The National Aeronautics And Space Administration | Zero-Valent Metallic Treatment System and its Application for Removal and Remediation of Polychlorinated Biphenyls (PCBs) |
US8288307B2 (en) | 2006-05-19 | 2012-10-16 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds |
US7842639B2 (en) | 2006-05-19 | 2010-11-30 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds |
US20110172082A1 (en) * | 2006-05-19 | 2011-07-14 | United States of America as represented by the Administrator of the National Aeronautics and | Mechanical Alloying of a Hydrogenation Catalyst Used for the Remediation of Contaminated Compounds |
US20070287628A1 (en) * | 2006-05-19 | 2007-12-13 | Usa As Represented By The Administrator Of The National Aeronautics And Space Adm | Mechanical Alloying of a Hydrogenation Catalyst Used for the Remediation of Contaminated Compounds |
WO2007136757A3 (en) * | 2006-05-19 | 2008-01-10 | Usa As Represented By The Admi | Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds |
WO2007136757A2 (en) * | 2006-05-19 | 2007-11-29 | Usa As Represented By The Administrator Of The National Aeronautics And Space Administration | Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds |
CN104143625A (en) * | 2007-07-06 | 2014-11-12 | 索尼株式会社 | ANODE MATERIAL, ANODE, BATTERY, AND METHODS OF MANUFACTURING the anode material, the anode and the battery. |
US9196904B2 (en) * | 2009-02-03 | 2015-11-24 | Imerys Graphite & Carbon Switzerland Sa | Graphite material |
US20120077035A1 (en) * | 2009-02-03 | 2012-03-29 | Timcal S.A. | New graphite material |
US9997764B2 (en) * | 2009-02-03 | 2018-06-12 | Imerys Graphite & Carbon Switzerland Sa | Processes for treating graphite and graphite materials |
US9666854B2 (en) * | 2009-02-03 | 2017-05-30 | Imerys Graphite & Carbon Switzerland Sa | Graphite material |
US20120258374A1 (en) * | 2009-09-10 | 2012-10-11 | The University Western Australia | Process for Producing Hydrogen from Hydrocarbons |
US20160156051A1 (en) * | 2009-09-10 | 2016-06-02 | Hazer Group Ltd | Process for producing hydrogen from hydrocarbons |
US10629933B2 (en) | 2009-09-10 | 2020-04-21 | Hazer Group Ltd | Process for producing hydrogen from hydrocarbons |
US20150179298A1 (en) * | 2012-06-14 | 2015-06-25 | Hexcel Composites Limited | Composite materials |
US20140217332A1 (en) * | 2012-06-14 | 2014-08-07 | Hexcel Corporation | Composite materials |
US20170047581A1 (en) * | 2014-02-11 | 2017-02-16 | Batelle Memorial Institute | Additives to enhance electrode wetting and performance and methods of making electrodes comprising the same |
CN108367927A (en) * | 2015-12-09 | 2018-08-03 | 同和电子科技有限公司 | The coating graphite particle of silver, the coating graphite mixed powder of silver and its manufacturing method and electrocondution slurry |
US20180362348A1 (en) * | 2015-12-09 | 2018-12-20 | Dowa Electronics Materials Co., Ltd. | Silver-Coated Graphite Particles, Silver-Coated Graphite Mixed Powder and Production Method Therefor, and Conductive Paste |
US10773961B2 (en) * | 2015-12-09 | 2020-09-15 | Dowa Electronics Materials Co., Ltd. | Silver-coated graphite particles, silver-coated graphite mixed powder and production method therefor, and conductive paste |
US11380895B2 (en) * | 2017-04-03 | 2022-07-05 | The George Washington University | Methods and systems for the production of crystalline flake graphite from biomass or other carbonaceous materials |
US10950860B2 (en) * | 2017-09-14 | 2021-03-16 | Toyota Jidosha Kabushiki Kaisha | Graphite material for negative electrode of lithium ion secondary cell and method for producing the same |
US20210316994A1 (en) * | 2018-08-31 | 2021-10-14 | Zhanjiang Juxin New Energy Co., Ltd | Spherical Graphite for Lithium Battery and Preparation Method thereof |
CN109503166A (en) * | 2018-09-29 | 2019-03-22 | 东莞市凯金新能源科技股份有限公司 | A kind of flatbed lithium ion battery graphite cathode material and preparation method |
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JP4610851B2 (en) | 2011-01-12 |
DE60108163D1 (en) | 2005-02-03 |
CA2324431A1 (en) | 2002-04-25 |
US9312537B2 (en) | 2016-04-12 |
US20130011554A1 (en) | 2013-01-10 |
ATE285989T1 (en) | 2005-01-15 |
JP2014028753A (en) | 2014-02-13 |
US20070071669A1 (en) | 2007-03-29 |
WO2002034670A1 (en) | 2002-05-02 |
AU2002213710A1 (en) | 2002-05-06 |
US20100092808A1 (en) | 2010-04-15 |
DE60108163T2 (en) | 2005-12-08 |
JP2009184915A (en) | 2009-08-20 |
US20160141603A1 (en) | 2016-05-19 |
US20130323600A1 (en) | 2013-12-05 |
EP1334065B1 (en) | 2004-12-29 |
US9412999B2 (en) | 2016-08-09 |
CA2422660A1 (en) | 2002-05-02 |
EP1334065A1 (en) | 2003-08-13 |
CA2422660C (en) | 2011-06-14 |
US9444092B2 (en) | 2016-09-13 |
JP5740079B2 (en) | 2015-06-24 |
JP2004511422A (en) | 2004-04-15 |
US9184437B2 (en) | 2015-11-10 |
US20160060119A1 (en) | 2016-03-03 |
US9508983B2 (en) | 2016-11-29 |
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