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 PDF

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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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Prior art keywords
particles
graphite
graphite particles
impurities
modified
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Abdelbast Guerfi
Fernand Brochu
Kimio Kinoshita
Karim Zaghib
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Hydro Quebec
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Assigned to HYDRO-QUEBEC reassignment HYDRO-QUEBEC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BROCHU, FERNARND, GUERFI, ABDELBAST, ZAGHIB, KARIM, KINOSHITA, KIMIO
Publication of US20040053050A1 publication Critical patent/US20040053050A1/en
Priority to US11/606,231 priority Critical patent/US20070071669A1/en
Priority to US12/572,510 priority patent/US9444092B2/en
Priority to US13/617,084 priority patent/US9312537B2/en
Priority to US13/857,861 priority patent/US9184437B2/en
Priority to US14/878,742 priority patent/US9412999B2/en
Priority to US14/933,436 priority patent/US9508983B2/en
Abandoned legal-status Critical Current

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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.

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US20160060119A1 (en) 2016-03-03
US20130323600A1 (en) 2013-12-05
EP1334065B1 (fr) 2004-12-29
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US9184437B2 (en) 2015-11-10
US20100092808A1 (en) 2010-04-15
CA2324431A1 (fr) 2002-04-25
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US9508983B2 (en) 2016-11-29
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ATE285989T1 (de) 2005-01-15
US9312537B2 (en) 2016-04-12
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JP4610851B2 (ja) 2011-01-12
US9444092B2 (en) 2016-09-13
US20070071669A1 (en) 2007-03-29
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US20160141603A1 (en) 2016-05-19
WO2002034670A1 (fr) 2002-05-02

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