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• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
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  • H01M4/043—Processes of manufacture in general involving compressing or compaction
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• • H—ELECTRICITY
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/134—Electrodes based on metals, Si or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
  • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
  • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/362—Composites
  • H01M4/366—Composites as layered products
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/386—Silicon or alloys based on silicon
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—Electric conductive fillers
  • H01M4/625—Carbon or graphite
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/021—Physical characteristics, e.g. porosity, surface area
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the invention relates generally to particulate materials having high electrochemical energy storage capacities. More specifically the invention relates to particulate anode materials comprising elements of group IVa, preferably silicon, oxides thereof or alloys thereof.
• the materials according to the invention can have deposited thereon conductive carbon. Methods for their preparation involve dry and wet grinding steps.
• Lithium-ion batteries have shown technical success and commercial growth since the initial work by Sony in the early 90's based on lithium insertion electrodes; essentially consisting of high voltage cobalt oxide cathode invented by J.B. Goodenough (U.S. 5,910,382 and U.S. 6,391 ,493) and carbon anode using coke or graphitized carbonaceous materials.
• lithium-ion batteries have progressively replaced existing Ni-Cd and Ni-MH batteries, because of their superior performances in most portable electronic applications.
• Ni-Cd and Ni-MH batteries because of their superior performances in most portable electronic applications.
• cost and intrinsic instability under abusive conditions, especially in their fully charged state only small size and format cells have been commercialized with success.
• silicon (Si) reversibly absorbs (intercalates) and desorbs (deintercalates) lithium ions through the reaction between silicon and lithium, and has a maximum theoretical capacity of about 4200 mAh/g (9366 mAh/cc, a specific gravity of 2.23) that is substantially higher than that of carbonaceous materials and thereby is promising as a high-capacity anode material.
• Silicon-based anodes theoretically offer as much as a ten-fold capacity improvement over graphite. However, silicon-based anodes have not been stable enough to cycling for practical use.
• One way of improving the cycle performance of silicon-based anodes is to reduce the size of the particles in the material used in the fabrication of the anode. Coating of the particles in the material used with carbon has also been found beneficial. The smaller size helps to control the volume change and stresses in the Si particles.
• the carbon coating on the silicon surface acts like an electrical pathway so that even when there is a volume change, contact is not lost with the current collector.
• Silicon is produced industrially by carbothermal reduction of silicon dioxide (quartzite) with carbon (coal, charcoal, petroleum coke, wood) in arc furnaces by a reaction that in an idealized form can be written as:
• the available raw materials are not pure and the product generally contains other elements, such as Fe, Al, Ca and Ti.
• the product With pure operation and pure raw materials and electrodes, it is possible to obtain silicon with less than 1-2% percent of other elements.
• This product is traditionally called metallurgical grade silicon metal even though solid silicon is not a metal.
• metallurgical treatments like gas blowing (dry air, C1 ⁇ 2, C ) may reduce alkaline species (K, Na, Mg, Ca, Al, Sr) at temperatures higher than 1410°C. Those species will either be volatized from the liquid metal surface or be physically separated in a slag phase. If transition elements such as Fe, Ti, Cu, Cr, Mn, V, Ni, Zn, Zr, etc. need to be reduced, directional solidification may be used. Another efficient method consists of finely grinding solid silicon and expose the intermetallic phases to acid (HF, HCI, H2SO4 or a mixture). With those metallurgical treatments, the silicon metal purity can reach 99.999% (5N purity level).
• Silicon-based anode materials can be prepared at low cost from solid crystalline ingots or micron size powders by conventional grinding process (jaw crusher, cone crusher, roll crusher, jet mill, etc.). Mechanical attrition process is one of the most used processes to produce fine particles. Industrial wet nano- grinding bead mill equipment is available commercially, which can be used to reduce particle size down to 10 to 20 nm; see for example WO 2007/100918 for lithium metal phosphate ultrafine grinding. These techniques are especially useful for high purity Si.
• the inventors have designed a method for the preparation of a particulate material which comprises an element of group IVa, preferably silicon, an oxide thereof or an alloy thereof.
• the method involves dry and wet grinding steps to yield nanometer size particles.
• the nanometer size particles can be coated with conductive carbon.
• the element of group IVa can be Si.
• the alloy can comprise at least one of Li, Al, Mg, Fe, Ge, C, Bi, Ag, Sn, Zn, B, Ti, Sr, P and O.
• the material prepared by the method according to the invention is used as anode.
• the invention provides the following:
• the alloy comprises at least one of Li, Al, Mg, Fe, Ge, C, Bi, Ag, Sn, Zn, B, Ti, Sr, P and O.
• an amount of the alloying elements is about 2%wt or less of the particulate material.
• step (a) is performed in a bead mill, preferably using zirconia beads; a puck and ring mill; a jet mill; or a cyclone mill.
• step (e) is performed at a temperature of about 600-800°C, preferably about 650-750°C, more preferably about 730°C.
• step (e) is performed at a rate of about 3-10°C/min, preferably about 6°C/min.
• step (21 ) A method according to (7), (19) or (20) above, wherein step (e) is performed during a period of about 30 minutes to 2 hours, preferably about 1 hour.
• step (e) is performed under inert atmosphere, preferably argon atmosphere.
• Figure 1 shows a process flow diagram illustrating the method according to the invention.
• Figure 2 shows a graph of the particles size distribution obtained from laser scattering analyzer observations (LA-950V2, Horiba) of a sample of micrometer size particles according to the invention.
• Figure 3 shows the evolution of the average particle size (dso) over time during dry grinding.
• Figure 4 shows a graph of the particle size distribution obtained from laser scattering analyzer observations (LA-950V2, Horiba) of a further sample of micrometer size particles according to the invention.
• Figure 5 shows a graph of the particle size distribution obtained from laser scattering analyzer observations (LA-950V2, Horiba) of still a further sample of micrometer size particles according to the invention.
• Figure 6 shows the evolution of the average particle size (dso) over time during wet grinding.
• Figure 7 shows a graph of the particle size distribution obtained from laser scattering analyzer observations (LA-950V2, Horiba) of a sample of nanometer size particles according to the invention.
• Figure 8 shows the evolution of the average particle size (dso) over time during a further wet grinding.
• Figure 9 shows a graph of the particle size distribution obtained from laser scattering analyzer observations (LA-950V2, Horiba) of a further sample of nanometer size particles according to the invention.
• Figure 10 shows voltages profiles of the Li/Si composite anode in 1 M UPF6-EC-DEC.
• the inventors have designed a method for the preparation of a particulate material which comprises an element of group IVa, preferably silicon, an oxide thereof or an alloy thereof.
• the method involves dry and wet grinding steps to yield nanometer size particles.
• the nanometer size particles can be coated with conductive carbon.
• the element of group IVa can be Si.
• the alloy can comprise at least one of Li, Al, Mg, Fe, Ge, C, Bi, Ag, Sn, Zn, B, Ti, Sr, P and O.
• the material prepared by the method according to the invention is used as anode.
• the element of group IVa is Si or the oxide is an Si oxide (SiOx).
• a process flow diagram of the method according to the invention is outlined in Figure 1.
• a method for preparing a particulate Si material, wherein at least part of the surface of the particles can be coated with conductive carbon comprises the following steps: (a) dry grinding Si particles from an ingot of Si or SiO x to obtain micrometer size particles; and (b) wet grinding the micrometer particles dispersed in a solvent carrier to obtain nanometer size particles having a size between 10 to 100 nanometers.
• a stabilizing agent can be added during or after the wet grinding step. Such agent helps in avoiding agglomeration of the particles. Also, it allows for an effective dispersion of the particles in the solvent carrier.
• Suitable stabilizing agents are described for example in WO 2008/067677. They are generally commercially available and include for example surface active agents such as surfactants. As will be understood by a skilled person, any other suitable stabilizing agent can be used.
• the method can comprise the further step of (c) drying the nanometer size particles.
• the method can comprise the further steps of: (d) mixing the nanometer size particles obtained either in step (b) or in step (c) with a carbon precursor; and (e) pyrolysing the mixture, thereby forming a coat of conductive carbon on at least part of the surface of the particles.
• the Si particles used in step (a) are millimeter size particles which can be obtained by the following steps: (a1) providing commercially available metallurgical grade Si; (a2) melting the Si; (a3) casting and cooling the melted Si to obtain ingots; and (a4) crushing the ingots to obtain the millimeter size Si particles.
• Melting of the starting material can be performed in an induction furnace using a graphite crucible.
• any other suitable means for melting can be used in the process.
• the melting process is performed under inert atmosphere wherein an inert gas such as for example argon, is used.
• the temperature of the melted Si is raised to about 1410-1650°C, preferably about 1450°C, and then it is casted in a mould and cooled to room temperature.
• a suitable mould type used in the process can be for example a graphite mould; however, as will be understood by a skilled person any other suitable mould type can be used.
• Ingots formed after cooling the melted Si are crushed into centimeter size particles, then into millimeter size particles.
• the crushing can be performed using a jaw crusher which can have an abrasion resistant liner, such as zirconia or tungsten carbide. Such crushing will generally yield centimeter size particles which are further ground into millimeter size particles using for example a roll crusher.
• dry grinding of the millimeter size Si particles into micrometer particles can be performed for example in a jet mill, a bead mill, a puck and ring mill, or a cyclone mill.
• any other suitable grinding means can be used.
• Beads used with a bead mill can be for example 5 mm zirconia beads.
• micrometer size Si particles are dispersed into a solvent carrier then subjected to grinding
• the solvent carrier can be an organic solvent.
• the carrier solvent can be an alcohol such as a C1-C12 alcohol or water.
• the micrometer size particles were dispersed in isopropanol or furfuryl alcohol; however as will be understood by a skilled person, any other suitable solvent can be used in the process.
• the solvent carrier is used in an amount of about 5-20%wt, preferably about 8-15%wt, more preferably about 10%wt of the amount of Si.
• the nanometer size Si particles can further be mixed with a carbon precursor (step (c) outlined above).
• the particles are in wet form, i.e. still in the solvent carrier (particles obtained from step (b) outlined above).
• the particles are in wet form (particles obtained from step (c) outlined above).
• the carbon precursor is intimately mixed with the Si particles in order to achieve impregnation of the particles surface such that after pyrolysis (step (e) outlined above), the conductive carbon deposited is in intimate contact with the particles.
• the carbon precursor can be an organic carbon precursor.
• the carbon precursor can be for example a cross-linkable monomer, oligomer, polymer or copolymer, preferably poly(maleic anhydride-1 -alt-octadecene).
• any suitable material capable of being adsorbed on the surface of the nanometer size Si particles such as to leave thereon after pyrolysis a layer of conductive carbon, can be used in the process.
• the amount of carbon precursor used can be for example about 2-10%wt, preferably about 5%wt of the amount of Si.
• This step allows for burning of the carbon precursor and deposit of a layer of conductive carbon on the surface of the nanometer size Si particles.
• the conductive carbon deposited is preferably non- powdery.
• pyrolysis of the mixture is performed at a temperature of about 600- 800°C, preferably about 650-750°C, more preferably about 725°C.
• the drying rate during pyrolysis can be for example about 3-10°C/min., preferably about 6°C/min.
• the drying time can be for example about 30 minutes to 2 hours, preferably about 1 hour.
• This step can be conducted under inert atmosphere such as for example argon atmosphere.
• a subsequent step of cooling the pyrolyzed mixture is performed. This step is conducted at a cooling rate of about 2°C/min.
• the invention provides according to an aspect, for a particulate Si material which is prepared by the method according to the invention and as described above.
• a mean size of the particles is about 10-100 nm, preferably about 50-90 nm, more preferably about 70 nm.
• the material has a carbon content of about 0.5-10%wt, preferably about 2-5%wt.
• the invention provides according to another aspect, for an anode which is fabricated using the material according to the invention and as described above.
• the invention provides according to yet another aspect, for an electrochemical cell or an electrochemical storage energy apparatus which comprises the anode according to the invention and as described above.
• the invention provides according to a further aspect, for an electrochemical storage energy apparatus comprising the anode according to the invention and as described above.
• the electrochemical storage apparatus can be a lithium-ion battery, a silicium-air battery or a polymer battery.
• Example 3 The millimeter size particles from Example 3 were ground on a bead mill (PV-250, Hosokawa) using 5 mm zirconia beads to achieve micrometer size particles.
• Laser scattering analyzer observations (LA- 950V2, Horiba) show that dry milling leads to micrometer size primary particles in the range of 0.3 ⁇ - 3 ⁇ ( Figure 2).
• Example 5
• Example 3 The millimeter size particles from Example 3 were ground by using a cyclone mill (150BMW,
• micrometer size powder from Example 6 was dispersed in isopropyl alcohol (IPA) solution at 10%w of solid concentration in the presence of a Triton 100X surfactant agent (0.5%wt to solid) and then ground on a bead mill (SC100/32-ZZ mill, Nippon Coke) using 0.3 mm zirconia beads to achieve nanometer size particles (Figure 6).
• IPA isopropyl alcohol
• Example 10 The experiment was conducted as outlined above in Example 7 with a difference that the micrometer size powder was dispersed in cyclohexane (instead of IPA). After wet milling, the particle size was in the range of 80nm - 180nm after 700 minutes.
• cyclohexane instead of IPA
• a solution of poly(maleic anhydride-1-alt-octadecene) dissolved in IPA is mixed with the Si in IPA, in a ratio of 5%wt poly(maleic anhydride-1-alt-octadecene) over Si.
• the mixed solution was stirred thoroughly and then dried at room temperature by blowing with dry air while stirring.
• the dried powder is heated to 725°C at 6°C/min and held for 1 h at 725°C in a rotary kiln under argon flow, and then cooled at a cooling rate of 2°C/min. After this treatment, large aggregates of carbon coated nanoparticles having a mean size of 50-200 nm are obtained.
• the pyrolytic carbon content is 1.4%, as measured by a C, S analyzer (LECO method). The product thus obtained is designated by C-Si.
• the anodes were prepared by mixing the Si powder with carbon conductor and alginate Water-soluble binder and H2O. Thereafter, the slurry was applied to the copper foil and dried at 120°C in vacuum for 12h. The electrochemical characterization was performed in coin-type cell with lithium metal as anode in 1 M UPF6-EC-DEC. Three anodes composite electrodes were evaluated; dry milled Si (Example 4), nano-Si in IPA (Example 8) and nano-Si in cyclohexane (Example 9). The cells were cycled between 2.5V and 10mV. The first discharge in Figure 10 shows that the particle size affects the voltage profile of the cell.
• the mean voltage was gradually increased when the particle size decreased: 35mV for Si-dry milled (0.3-3.0 ⁇ ), 78mV for nano-Si-Cyclohexane (80-180 nm) and 92 mV for nano-Si-IPA (50-150mV). Reducing the particle size improves performance of this material and also increases slightly the discharge voltage from zero volt, which indicates that the safety of the battery is improved.

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