Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
  • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F31/00—Mixers with shaking, oscillating, or vibrating mechanisms
  • B01F31/80—Mixing by means of high-frequency vibrations above one kHz, e.g. ultrasonic vibrations
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B32/00—Carbon; Compounds thereof
  • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
  • C09D105/04—Alginic acid; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/52—Electrically conductive inks
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• • 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
  • 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
  • H01M4/626—Metals
• • 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
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/027—Negative electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0025—Organic electrolyte
  • H01M2300/0028—Organic electrolyte characterised by the solvent
  • H01M2300/0037—Mixture of solvents
• • 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
  • H01M4/36—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
• • 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 to a composite material comprising nano-objects, in particular carbon nano-objects.
• the invention relates to a composite material comprising carbon nano-objects and nano-objects of a material other than carbon such as silicon.
• the material according to the invention could thus also be called nanocomposite material.
• the invention particularly relates to a composite material comprising carbon nanotubes (NCT or Carbon NanoTubes CNT in English) and silicon nanoparticles.
• the invention further relates to a process for preparing said composite material.
• the invention also relates to an ink comprising the composite material according to the invention.
• the composite material according to the invention such as a silicon / carbon composite material may in particular be used, after carbonization, as an electrochemically active electrode material, in particular a negative electrode, in electrochemical systems with organic electrolyte, non-aqueous, such as rechargeable electrochemical accumulators with organic electrolyte, especially in lithium batteries and even more precisely in lithium ion batteries.
• the invention therefore also relates to an electrode, in particular a negative electrode comprising this carbonized composite material as an electrochemically active material.
• the invention finally relates to an electrochemical system, for example a lithium ion accumulator comprising such an electrode.
• the technical field of the invention may, in general, be defined as that of composite materials comprising carbon and another material such as silicon.
• Lithium technology offers the best features compared to other technologies present.
• the lithium element is the lightest and most reductive metal and electrochemical systems using lithium technology can reach voltages of 4V against 1.5V for other systems.
• Lithium ion batteries have a specific energy density of 200 Wh / kg against 100 Wh / kg for NiMH technology, 30 Wh / kg for lead, and 50 Wh / kg for NiCd.
• active electrode materials consist of an electrochemically active material which constitutes a host structure in which the cations, for example lithium cations, are inserted and disintegrated during cycling.
• the most commonly used negative electrode active material in lithium ion batteries is graphite carbon, but has a low reversible capacitance and exhibits an irreversible loss of capacitance "ICL".
• Carbon nanotubes have been used as additives for active negative electrode or positive electrode materials, or as anode active material to improve the performance of lithium ion batteries.
• CNT Carbon nanotube
• carbon nanotubes can be used as anode material in place of graphite, and discloses nanocomposite anode materials comprising single-wall carbon nanotubes and various anode active materials such as Sn ; Bi; SnSb; CoSb 3 ; Ag, Fe, and Sn; Ti0 2 ; Sn0 2 ; Li 4 Ti 5 O 12; transition metal oxides such as TiO 2 , Co 3 O 4 , CoO, and Fe 3 O 4 ; and finally silicon.
• anode active materials such as Sn ; Bi; SnSb; CoSb 3 ; Ag, Fe, and Sn; Ti0 2 ; Sn0 2 ; Li 4 Ti 5 O 12; transition metal oxides such as TiO 2 , Co 3 O 4 , CoO, and Fe 3 O 4 ; and finally silicon.
• silicon is a desirable alternative to carbon as negative electrode material. Nevertheless, this material has a major disadvantage preventing its use. In fact, the volume expansion of the silicon particles, which can reach up to 400% during charging during the insertion of the lithium (Li-ion system), leads to a degradation of the material with the cracking of the particles and the detachment of these of the current collector.
• CN-A-101439972 [2] describes particles of a silicon-carbon composite material which comprises carbon nanotubes bonded to silicon nanoparticles by amorphous carbon.
• This composite material is prepared by a process comprising the following successive steps:
• the silicon nanoparticles and the carbon nanotubes are dispersed in a solvent such as water or ethanol, in the presence of a dispersing agent;
• the solvent and the dispersing agent are removed to thereby obtain particles of a composite material comprising silicon nanoparticles and carbon nanotubes;
• the particles of this composite material are brought into contact with a solution of an amorphous carbon precursor in an organic solvent;
• the solvent is removed from the precursor and the carbonization of the precursor is carried out by a chemical vapor deposition (CVD) process.
• the amorphous carbon precursor is an organic compound selected from resins, asphalts, sugars, benzene, and naphthalene.
• the statistical mixture is defined as an isoprobability of assembling a carbon nanotube (CNT, NTC) to a silicon particle (P to assemble a silicon particle to a carbon nanotube (P), to assemble a silicon particle to a silicon particle (Psi-s, or to assemble a carbon nanotube to a carbon nanotube (P C NT-cN-r) - the statistical mixture corresponds to an equality of the assembly probabilities, that is, PP Psi-si ⁇ P
• the statistical mixture is not optimal, it does not make it possible to generate the specific "cluster" structure of the composite material according to the invention.
• To obtain the specific "cluster” structure of the material according to the invention it is necessary that
• the amorphous carbon content of the composite material prepared in this document is at least about 24%, which is very high for use as a negative electrode active material in lithium ion batteries.
• the process described in this document also has the drawback of using three organic molecules: one as a dispersing agent, one as an organic solvent and one as an amorphous carbon precursor.
• nanocomposite material comprising nano-objects, in particular a nanocomposite material comprising carbon nano-objects, in particular carbon nanotubes, and nano-objects of a a material other than carbon, in particular silicon nanoparticles, which when used as an electrochemically active material in an accumulator such as a lithium ion accumulator, makes it possible to obtain improved performance, particularly as regards the discharge capacity of these accumulators.
• the purpose of the present invention is, among others, to meet these needs.
• the object of the present invention is in particular to provide a nanocomposite material comprising nano-objects, in particular a nanocomposite material comprising carbon nano-objects, such as carbon nanotubes and nano-objects of a material other than carbon. , which does not have the disadvantages, defects, limitations and disadvantages of the nanocomposite materials of the prior art, as represented in particular by the documents studied above, and which solves the problems of the materials of the prior art.
• the object of the present invention is still to provide a process for the preparation of such a nanocomposite material which likewise does not have the disadvantages, defects, limitations and disadvantages of the processes for preparing nanocomposite materials of the prior art.
• a nanocomposite material comprising nano-objects in at least a first electronically conductive material and nano-objects or submicron objects in at least a second material. different from the first material; said nanocomposite material comprising nanostructures each constituted by a three-dimensional network constituted by the nano-objects in at least one first electron-conducting material bonded and maintained by a polysaccharide, the nano-objects or submicron objects in at least one second material different from the first material being self-assembled around said network and being fixed to the nano-objects in at least a first electronically conductive material by said polysaccharide, and said nanostructures being homogeneously distributed in the material.
• nano-objects in at least one first material it is meant that the nano-objects consist of a single first material or several first materials.
• nano-objects or submicron objects in at least one second material means that these nano-objects or submicron objects are constituted by a single second material or by several second materials.
• nanostructures are evenly distributed, evenly throughout the volume of the material and that their concentration, presence, are substantially the same throughout the volume of the material.
• the second material is not necessarily an electronically conductive material, and that it can often be an insulating material.
• each of the nanostructures has a size that is at least equal to the size of each of the nano-objects in at least one first electronically conductive material, for example the length of the carbon nanotubes.
• Each of the nanostructures can thus have a size of 1 ⁇ to 10 ⁇ .
• the content of nano-objects in at least one first electronically conductive material and nano-objects or submicron objects in at least one second material different from the first material is respectively from 1% to 40%, and from 60% to 99% by weight .
• the first electronically conductive material is selected from carbon, metals such as aluminum and copper, and metal alloys such as aluminum and copper alloys.
• the second material may be selected from silicon; metals such as tin; metal alloys; sulfur, metal oxides such than alumina; positive electrode active materials of lithium ion accumulators such as LiFePO 4 , LiFeSO 4 F, LiCoO 2 , LiNiO 2 , LiFe x Mn y PO 4 , LiMn x Ni y O 4 , LiMn x Ni , Nb z 0 4 , LiNi x Mn y Al z O 2 , LiCo x Ni y Mn z 0 2 , titanium phosphates, Li 2 CoSiO 4 , LiMn x O 4 , LiNi x PO 4 , LiCo x O 2 , LiNi x Co y 0 2 sodium, vanadium oxide, TiS 2 , TiO x S z , Li 2 MnO 3 ; and the active materials for negative electrode of lithium ion batteries such as graphite, titanates such as Li LiF
• the nano-objects in at least one first material may be selected from nanotubes, nanowires, nanofibers, nanoparticles, nanocrystals in at least a first material, and mixtures thereof; and the nano-objects or submicron objects in at least one second material may be selected from nanotubes, nanowires, nanofibers, nanoparticles, submicron particles, nanocrystals in at least a second material, and mixtures thereof.
• the first material is carbon
• the second material is a material other than carbon such as silicon.
• the carbon nano-objects may be chosen from carbon nanotubes, carbon nanowires, carbon nanofibers, carbon nanoparticles, carbon nanocrystals, carbon blacks. , and mixtures thereof; and the nano-objects or submicron objects in at least one material other than carbon may be chosen from nanotubes, nanowires, nanofibers, nanoparticles, submicron particles, nanocrystals in at least one material other than carbon, and their mixtures.
• the nano-carbon objects may be chosen from carbon nanotubes and carbon nanofibers; and nano-objects or submicron objects in at least one material other than carbon may be nanoparticles or submicron silicon particles.
• the carbon nanotubes may be chosen from single-walled carbon nanotubes, and multi-walled carbon nanotubes such as double-walled carbon nanotubes.
• nano-objects or submicron objects in at least one material other than carbon may have a spherical or spheroidal shape.
• the first material is aluminum or copper
• the second material is a material other than aluminum or copper such as silicon.
• the nano-objects of aluminum or copper may be chosen from aluminum or copper nanowires; and the nano-objects or submicron objects in at least one material other than aluminum or copper may be chosen from nanotubes, nanowires, nanofibers, nanoparticles, submicron particles, nanocrystals in at least one other material than aluminum or copper such as silicon.
• the ratio of the number of nano-objects or submicron objects in at least one second material, for example silicon, to the number of nano-objects in at least one first material, for example carbon, such as carbon nanotubes is less than or equal to 1/100.
• the polysaccharide may be chosen from pectins, alginates, alginic acid, and carrageenans.
• the material according to the invention is in the form of a powder.
• this powder is an extremely aerated powder, expanded, very sparse, with a large apparent volume, generally greater than 18 liter / kg of powder.
• this powder has a mean particle size, which generally corresponds to the average size of the nanostructures or clusters, of between 1 ⁇ and 100 ⁇ , for example 20 ⁇ , a specific surface area of between 10 m 2 / g and 50 m 2 / g. and a density of between 2.014 g / cm 3 and 2.225 g / cm 3 .
• the invention furthermore relates to the material obtained by carbonization of the composite material as described above and conversion of the polysaccharide to amorphous carbon.
• This carbonaceous material has an amorphous carbon content which is generally from 1% to 5% by weight, which is lower than the amorphous carbon content of the material of the document [2].
• grape bunches of the composite material according to the invention is preserved in the carbonized material.
• the composite material according to the invention has never been described or suggested in the prior art. It is the same material obtained by carbonization of the material according to the invention.
• the composite material according to the invention has a very specific structure with a three-dimensional network constituted by the nano-objects of the first material, such as carbon, bonded and maintained by a polysaccharide, the nanoparticles of the second material, such as a material other than carbon, being self-assembled around said network and being attached to the nano-objects of the first material, such as carbon by said polysaccharide.
• Such a structure for a nanocomposite material based on nano-objects such as carbon nano-objects, for example carbon nanotubes, is completely new.
• the very specific structure or organization of the material according to the invention can be defined as a "grape bunch" structure or organization in which the nano-objects in a first material, such as carbon, for example carbon nanotubes, form a three-dimensional network or skeleton around which come Agglomerate, aggregate, self-assemble, the nano-objects into a second material, for example a material other than carbon, such as silicon nanoparticles.
• a first material such as carbon, for example carbon nanotubes
• a second material for example a material other than carbon, such as silicon nanoparticles.
• Nano-objects in a first material for example nano-objects in carbon such as NTCs form the branch and peduncle of the cluster, while nano-objects in a second material, for example in a second material other that carbon (in the case where the first material is carbon), such as nanoparticles of silicon form the grapes.
• a first material for example nano-objects in carbon such as NTCs form the branch and peduncle of the cluster
• nano-objects in a second material for example in a second material other that carbon (in the case where the first material is carbon)
• nanoparticles of silicon form the grapes.
• the nanocomposite material according to the invention is fundamentally different from the nanocomposite materials and in particular from the silicon / carbon nanocomposite materials of the prior art in that in the material according to the invention, the nano-objects in a first material, for example nano- carbon objects such as NTCs and nano-objects in a second material, for example a material other than carbon, such as silicon, are organized, whereas in the materials of the prior art the nano-objects are distributed randomly, statistically.
• a first material for example nano- carbon objects such as NTCs
• nano-objects in a second material for example a material other than carbon, such as silicon
• the organization of nano-objects in a first material, for example carbon nano-objects, and nano-objects of a second material, for example a material other than carbon, such as silicon is a very particular organization called "grape bunch" in which the nano-objects in a second material, such as a material other than carbon, are self-assembled around nano objects of a first material, for example carbon nano-objects, such as NTCs, which are used as electronically conductive skeleton.
• the material according to the invention has improved performance, for example in cycle, fast charging, when implemented in a lithium ion accumulator.
• the polysaccharide contained in the material according to the invention ensures in particular the formation and preservation of the structure, the specific organization in grape bunch of this material.
• the polysaccharide indeed plays several roles in the material according to the invention: it binds and holds the nano-objects in a first material, for example carbon nano-objects, which thus constitute a skeleton or three-dimensional network, and it ensures self-assembling the nano-objects into a second material, for example a material other than carbon, such as silicon, around said network, and fixing these nanoparticles to the nano-objects in a first material, such as the carbon.
• a first material for example carbon nano-objects, which thus constitute a skeleton or three-dimensional network
• a second material for example a material other than carbon, such as silicon
• the polysaccharide structures the ramifications of the network of nano-objects into a first material, for example nano-carbon objects, such as carbon nanotubes.
• a first material for example nano-carbon objects, such as carbon nanotubes.
• the polysaccharide first in the form of a hydrogel, then after lyophilization, keeps the nano-objects, such as nanotubes, in an expanded network.
• nano-objects of a second material for example a material other than carbon, such as silicon nanoparticles.
• the material according to the invention comprises an organized and connected network of nano-objects made of a first material, for example carbon nano-objects, such as carbon nanotubes "NTC", the connections between the nano objects in a first material, for example between carbon nano-objects, being provided by the polysaccharide molecules such as an alginate.
• a first material for example carbon nano-objects, such as carbon nanotubes "NTC”
• NTC carbon nanotubes
• nano-objects in a second material for example in a material other than carbon, such as silicon nanoparticles for example, are glued on the nano-objects in a first material, for example on nano-objects.
• carbon such as CNTs
• hydrogen bonds are formed between the hydroxyl groups on the surface of the nano-objects in a second material, for example in a material other than carbon, for example the silanol groups of the silicon nanoparticles, and OH groups of the polysaccharide, such as an alginate.
• hydroxyl groups are formed, such as silanol groups on the surface of nano-objects such as silicon nanoparticles.
• the polysaccharide such as an alginate which allows the good dispersion of the nano-objects in a first material, for example nano-objects of carbon during the preparation of the material, also allows the self-assembly of the nano-objects in a second material, and acts as a nanostructural "glue" which, when the material is used in a lithium ion accumulator, gives this material the necessary resistance to the electrolyte and the swelling of the material other than than carbon, such as silicon, which can exceed 240%.
• the structure, organization, in "bunch of grapes" of the material according to the invention unlike the materials in which the nano-objects are not organized in this way, makes it possible to retain the electronic conduction and the accessibility to the electrolyte , even when nano-objects or submicron objects in a second material, for example a material other than carbon, especially when it is silicon nanoparticles, see their volume increase.
• the structure, organization, in "bunch of grapes" of the material according to the invention also makes it possible to maintain the connectivity of nano-objects or submicron objects in at least a second material, for example in a material other than carbon, such as than silicon nanoparticles, to the three-dimensional electronic conductive network.
• the organization of the material according to the invention is retained and is not modified during an individual increase of the volume of the nano-objects in a second material, such as a material other than carbon (in the case where the first material is carbon), such as silicon nanoparticles.
• the invention furthermore relates to a process for the preparation of the nanocomposite material described above, in which the following successive steps are carried out:
• the nano-objects are brought into contact with at least one first material with water, and then the nano-objects are mixed in at least one first material with water using the succession, possibly repeated, of a ultrasonic mixing technique followed by a high-speed mixing technique, the mixing of nano-objects into at least one first material and water being kept in circulation, for example by a pump, such as a peristaltic pump, so as to prevent the nano-objects in at least one first material from becoming agglomerated, whereby obtain a dispersion consisting of nano-objects in at least one first material and water that is kept circulating.
• a pump such as a peristaltic pump
• this dispersion is an unstable mixture when the circulation stops, for example when the pump is stopped, such as a peristaltic pump, which conveys the mixture of nano-objects and water from the device.
• the ultrasonic mixing technique such as a disperser, mixer, ultrasonic, to the apparatus for implementing the mixture at high speed;
• the mixture is stopped by ultrasound and nano-objects or submicron objects are mixed in at least one second material with the dispersion consisting of nano-objects in at least a first material and using a high-speed mixing technique, whereby a dispersion consisting of nano-objects in at least one first material, nano-objects or submicron objects in at least one second material, and water is obtained that one keeps in circulation;
• At least one polysaccharide in the dispersion consisting of the nano-objects in at least one first material, nano-objects or submicron at least one second material, and water, and the polysaccharide is mixed with the dispersion using a high-speed mixing technique, whereby a dispersion is obtained in which nanostructures each constituted by a three-dimensional network are homogeneously distributed.
• nano-objects in at least a first material bonded and maintained by a hydrogel of the polysaccharide, the nano-objects or submicron objects in at least a second material being self-assembled around said network and being attached to the nano-objects in at least one first material by said polysaccharide hydrogel;
• the dispersion prepared in step c) is frozen, then the ice is sublimed by means of which the nanocomposite material according to the invention is obtained.
• the concentration of nano-objects in a first material, such as carbon nano-objects, in the dispersion of step a) is 1 to 5 g / L of water, for example 2.5 g / L of water.
• step a) the energy provided by the ultrasound does not exceed 5 Joules.
• the nano-objects or submicron objects in at least one second material have a size of 50 nm to 800 nm.
• the concentration of nano-objects or submicron objects in at least one second material in the dispersion of step b) is 5 to 15 g / l of dispersion, for example 10 g / l of dispersion.
• the concentration of the polysaccharide in the dispersion of step c) is from 1 to 6 g / l of dispersion.
• the process according to the invention comprises a specific sequence of specific steps which has never been described or suggested in the prior art and which allows the preparation of the material according to the invention having the structure and the specific properties set out above. .
• the method according to the invention comprises a series of simple steps, easy to implement.
• the process according to the invention does not use organic solvents because it uses water as the only solvent, more exactly a dispersion liquid.
• the only organic compound used in the process according to the invention is the polysaccharide, which can be considered to play to a certain extent the role of dispersion additive for nano-objects such as carbon nanotubes NTCs.
• the polysaccharide also plays the role of amorphous carbon precursor.
• the process according to the invention uses a single type of organic molecule, the polysaccharide, instead of three. Consequently, the amorphous carbon content of the material obtained by carbonization of the material obtained at the end of step d) and conversion of the polysaccharide to amorphous carbon is from 1% to 5% by mass, which is much lower than the minimum content of 24% of the material of the document [2].
• the invention further relates to an ink which comprises the composite material according to the invention, and a vehicle.
• the vehicle generally comprises at least one binder and at least one solvent.
• the ink may further comprise at least one electronic conductor.
• This electronic conductor may be chosen from graphite, graphene, carbon fibers, and mixtures thereof.
• the invention also relates to an electrode comprising as an electrochemically active material the composite material according to the invention in which the polysaccharide has been carbonized and converted into amorphous carbon.
• This electrode inherently has all the advantageous properties related to the composite material that it contains as an electrochemically active material.
• This electrode may be a positive electrode or a negative electrode.
• the invention further relates to an electrochemical system comprising such an electrode.
• This electrochemical system may be a non-aqueous electrolyte system such as a non-aqueous electrolyte rechargeable electrochemical accumulator.
• this electrochemical system is a lithium ion accumulator.
• This electrochemical system such as a lithium ion accumulator inherently has all the advantageous properties related to the electrode it contains.
• Figure 1 is a schematic side sectional view of the mixing device used to disperse the nano-objects in at least a first material such as carbon nano-objects, such as carbon nanotubes.
• FIG. 2 is a graph which shows the state of dispersion of the carbon nanotubes in the aqueous dispersion of carbon nanotubes obtained at the end of the first step of the process according to the invention implementing an ultrasonic mixing technique ( "US”) and a high-speed mixing technique (“Ultra-Turax").
• US ultrasonic mixing technique
• Ultra-Turax high-speed mixing technique
• Figure 3 is a photograph taken with the Scanning Electron Microscope (SEM) which shows the submicron silicon powder (diameter about 310 nm) of the company S'Tile °.
• SEM Scanning Electron Microscope
• the scale shown in FIG. 3 represents 1 ⁇ .
• Figure 4 is a graph which shows the characteristic curves of the particle size distribution of carbon nanotubes and silicon particles obtained at the end of the second step (b)) of the process according to the invention.
• Curve A is the particle size curve of a dispersion of carbon nanotubes comprising 1.25 g of NTCs in 0.5 liter of water, ie a concentration of NTCs of 2.5 g / l, to which were added 2 g of silicon particles (FIG. 3), ie a silicon concentration of 4 g / l and a concentration of carbon nanotubes of 2.5 g / l.
• Curve B is the particle size distribution of a dispersion in water (0.5 L) of carbon nanotubes at a concentration of 2.5 g / L, to which 4 g of silicon particles have been added (FIG. 3 ), a concentration of 8 g / L of silicon.
• Curve C is the particle size distribution of a dispersion in water (0.5 L) of 1.25 g of carbon nanotubes, ie a concentration of carbon nanotubes of 2.5 g / l, to which added 6 g of silicon particles (FIG. 3), ie a concentration of 12 g / l of silicon.
• Curve D is the particle size distribution curve of a dispersion (0.5 L) of carbon nanotubes at 2.5 g / L, to which 8 g of silicon particles (FIG. 3), a concentration of 16 g, have been added. g / L of silicon.
• FIG. 5 is a graph which shows the characteristic curves of the particle size of dispersions of carbon nanotubes and of "grape bunch" silicon particles to which alginate has been added, obtained at the end of the third step of FIG. process according to the invention.
• Curve A is the particle size distribution curve of a 1 liter solution in water containing a water dispersion of 1.25 g / L carbon nanotubes, to which 8.75 g of silicon in a solution of one liter in water, a silicon concentration of 8.75 g / L, and 2 g of alginate, an alginate concentration of 2 g / L.
• Curve B is the particle size distribution curve of a 1 liter solution in water containing a water dispersion of 1.25 g / L carbon nanotubes, to which 8.75 g of silicon and 4 g of alginate, ie a concentration of 8.75 g / l of silicon, and a concentration of 4 g / l of alginate.
• Curve C is the particle size distribution curve of a 1 liter solution in water containing a water dispersion of 1.25 g / L carbon nanotubes, to which 8.75 g of silicon, a concentration of 8.75 g / l of silicon, and 7.5 g of alginate, a concentration of 15 g / l of alginate.
• FIGs 6, 7, 8, and 9 are photographs, taken by Scanning Electron Microscope (SEM), which show the self-assembly in "bunch of grapes" of silicon particles around the network of carbon nanotubes in a powder of a material according to the invention obtained after having frozen and lyophilized a dispersion of carbon nanotubes and silicon particles to which alginate has been added.
• SEM Scanning Electron Microscope
• the scale shown in FIG. 6 represents 200 ⁇ .
• the scale shown in FIG. 7 represents 50 ⁇ .
• the scale shown in FIG. 8 represents 200 nm.
• the scale shown in FIG. 9 represents 3 ⁇ .
• FIG. 10 is a graph which shows the characteristic curves of the particle size of a dispersion of carbon nanotubes and particles of Lithium Iron Phosphate (LiFePO 4 ) "in a bunch of grapes” obtained at the end of the second step of FIG. process according to the invention, and dispersions of carbon nanotubes and particles of lithium iron phosphate (LiFePO 4 ) "grape bunch” to which was added alginate, obtained at the end of the third step of process according to the invention.
• LiFePO 4 Lithium Iron Phosphate
• Curve A is the granulometric curve of a solution of one liter in water containing a dispersion in water of carbon nanotubes at 2.5 g / L and particles of lithium iron phosphate (LiFePO 4 ) at 8.75 g / L.
• Curve B is the granulometric curve of a solution of one liter in water containing a dispersion in water of carbon nanotubes at 2.5 g / L and particles of lithium iron phosphate (LiFePO 4 ) at 8.75 g / L, to which was added 4 g of alginate, a concentration of 4 g / l of alginate.
• LiFePO 4 lithium iron phosphate
• Curve C is the particle size distribution curve of a one liter solution in water containing a dispersion in water of carbon nanotubes at 2.5 g / L and particles of lithium iron phosphate (LiFePO 4 ) at 8.75 g / L, to which were added 15 g of alginate, a concentration of 15 g / l of alginate.
• LiFePO 4 lithium iron phosphate
• FIG. 11 is a graph which shows the characteristic curves of the particle size of a dispersion of carbon nanotubes and "grape bunch” alumina particles obtained at the end of the second step of the process according to the invention, and dispersions of carbon nanotubes and "grape bunch” alumina particles to which alginate has been added, obtained at the end of the third step of the process according to the invention.
• Curve A is the granulometric curve of a one-liter solution in water containing a dispersion in water of carbon nanotubes at 2.5 g / l and alumina particles at 8.75 g / l.
• Curve B is the granulometric curve of a one-liter solution in water containing a dispersion in water of carbon nanotubes at 2.5 g / l and particles of alumina at 8.75 g / l at which was added 2 g of alginate, a concentration of 2/1 alginate.
• Curve C is the particle size curve of a solution of one liter in water containing a dispersion in water of carbon nanotubes at 2.5 g / l and of alumina particles at 8.75 g / l, to which were added 15 g / l of alginate, a concentration of 15 g / l of alginate.
• FIGS. 12 and 13 are photographs taken under a scanning electron microscope which show the structure of an electrode obtained from an ink prepared with the material according to the invention after plasma treatment.
• the scale shown in FIG. 12 represents 100 ⁇ .
• the scale shown in FIG. 13 represents 10 ⁇ .
• Figure 14 is a schematic side sectional view of a battery in the form of a button cell comprising for example a negative electrode to be tested according to the invention.
• FIG. 15 is a graph which gives the specific capacity (in mAh / g) in discharge as a function of the number of cycles (square markers) during the test (example 3) according to a C / 20 cycling of a button cell.
• a button cell such as that shown in Figure 14, whose positive electrode is composed of lithium metal and whose negative electrode comprises as a negative electrode active material a composite material according to the invention prepared in Example 1; as well as the specific capacity (in mAh / g) in discharge as a function of the number of cycles during the test (example 4) according to a C / 20 cycling of a button cell such as that represented in FIG.
• positive electrode is composed of lithium metal and whose negative electrode comprises as negative electrode active material a material not according to the invention (diamond markers ⁇ ) (see Example 4).
• Figure 16 is a photograph taken under a scanning electron microscope which shows the structure of an electrode according to the prior art prepared from a statistical dispersion of carbon nanotubes and silicon nanoparticles.
• the scale shown in FIG. 16 represents 1 ⁇ .
• FIG. 17 is a photograph taken under a scanning electron microscope which shows the structure of an electrode according to the invention in which the carbon nanotubes and the silicon nanoparticles have an organization in bunches of grapes.
• the scale shown in FIG. 17 represents 20 ⁇ .
• nano-objects we generally mean any single object or related to a nanostructure of which at least one dimension is less than or equal to 500 nm, preferably less than or equal to 300 nm, more preferably less than or equal to 200 nm, and better still less or equal to 100 nm, for example is in the range of 1 to 500 nm, preferably 1 to 300 nm, more preferably 1 to 200 nm, more preferably 1 to 100 nm, more preferably 2 to 100 nm, from 5 to 100 nm.
• nano-objects can be for example nanoparticles, nanowires, nanofibers, nanocrystals, or nanotubes.
• submicron object is generally meant any object whose size, such as the diameter in the case of a spherical or spheroidal object, is less than 1 ⁇ , preferably is 50 nm to 800 nm, for example 310 nm.
• nanostructure we generally mean an architecture consisting of an assembly of nano-objects and / or submicron objects which are organized with a functional logic and which are structured in a space ranging from cubic nanometer to cubic micrometer.
• polysaccharide is generally meant a polymeric organic macromolecule consisting of a chain of monosaccharide units.
• Such a macromolecule may be represented by a chemical formula of the form - [C x (H 2 0) y ] n-.
• macromolecules consisting of mannuronic acid (M-pattern) and guluronic acid (G-pattern) are preferably used according to the invention.
• the macromolecular chains most suitable for the invention are those which maximize the M units (that is to say that the ratio of M units / G units is greater than 60%), because they retain by coordination a greater amount of ions gelling the capsule.
• the composite material prepared by the process according to the invention is the positive or negative electrode active material of a lithium ion rechargeable battery, but it is quite obvious that the description which follows may easily be extended and adapted, where appropriate, to any application and any method of implementation of the composite material prepared by the process according to the invention.
• nano-carbon objects such as carbon nanotubes (CNTs) are dispersed in water.
• CNTs carbon nanotubes
• the solvent of the dispersion thus prepared consists exclusively of water, to the exclusion of any other solvent.
• the water of the dispersion is deionized water (“DI" water).
• Carbon nanotubes (“NTC” or “CNT” or Carbon Nanotubes in English language) may be single-walled carbon nanotubes (“SWCNT” or single wall carbon nanotubes in English language) or multi-walled carbon nanotubes (“MWCNT” or Multi Wall Carbon nanotubes in English language) such as double-walled carbon nanotubes ("DWCNT” or “Double Wall Carbon Nanotubes” in English).
• the carbon nanotubes may have an average length of 1 ⁇ to
• the concentration of carbon nano-objects in the dispersion is generally 1 to 5 g / L of water, for example 2.5 g / L of water.
• the maximum concentration not to be exceeded is estimated for 10 ⁇ tubes at 5 mg / ml of water.
• this first stage of dispersion of the carbon nanobonds can be done by adding the carbon nanobots to water and then submitting the nanoparticles.
• carbon objects in water to a mixing operation, dispersion, combining two mixing techniques namely an ultrasonic mixing technique and then a high-speed mixing technique.
• the ultrasound is generated by a probe placed in a container where the carbon nanotubes are placed in the water.
• Ultrasound generally has an acoustic power density of 1 to 1000 W / cm 2 , for example 90 W / cm 2, and carbon nano-objects, such as carbon nanotubes are exposed to the action of ultrasound for a period of time.
• short duration generally from 1 to 100 ms, for example 20 ms. Such a short duration makes it possible to disaggregate the nano-carbon objects without breaking them and thus prevents carbon nano-objects from being damaged.
• High speed mixing generally means that nano-objects of carbon in water are accelerated and sheared with a shear rate of 500 s 1 to 2000 s 1 and that the speed of nano-objects is generally 1 to 5 m / s, for example 3 m / s.
• This device comprises a high-speed mixing tank (1) and an ultrasonic reactor (2) specific for this purpose.
• the high-speed mixing tank (1) and the ultrasonic reactor (2) are in the form of circular cylindrical open vessels (3, 4).
• a first pipe (5) on which is placed a first pump, for example a peristaltic pump (6), connects an orifice (7) located in the center of the base (3) of the mixing tank at high speed (1). ) at the top of the ultrasonic reactor (2).
• a first pump for example a peristaltic pump (6)
• a second pipe (8) on which is placed a second pump (12), connects an orifice (9) located in the center of the base (4) of the ultrasonic reactor (2) at the top of the mixing tank at high speed (1).
• the diameter of the second pipe (8) is for example 6 mm.
• the flow velocity inside this pipe is estimated for example at 17 m / min for a flow rate greater than 0.5 l / min. It should be noted that, instead of using two pumps, it is possible to use a single two-way pump, for example the pump (6) which is then placed on the pipe (5) and on the pipe (8).
• the high-speed vessel (1) is equipped with a high-speed agitator (10), for example of U ltra Turrax ®.
• the mixing technique is a hybridization of the technique with the ultrasound technique by a probe.
• the ultrasonic probe or rod (11) is placed in the center of the ultrasonic reactor (2) opposite the orifice, outlet (9) located in the center of the base (4) of the ultrasonic reactor (2).
• water is first introduced into the mixing tank without the high-speed stirrer being actuated and then the carbon nano-objects, such as carbon nanotubes, are added. at the water.
• the carbon nano-objects are initially placed in the mixing tank without the high-speed agitator being actuated, and then water is added thereto.
• a mixture of nano-objects of carbon and water is thus formed.
• the na-carbon objects are predispersed, mixed beforehand and this predispersion, this mixture is placed in the tank (1).
• the mixture of water and nano-objects consists, for example, of 1.25 g of carbon nano-objects, for example NCTs, in 500 ml of deionized water, that is to say that the concentration of na no-objects of the mixture is 2.5 mg / ml.
• the mixture of water and nano-objects such as carbon nanotubes is conveyed via the pipe (5) under the action of the pump (6) and arrives in the ultrasonic reactor (2).
• the nano-objects are exposed to ultrasound emitted by the probe; for example they are exposed to ultrasound with a frequency of 20 kHz and a power of 250W for a short time, for example for about 20 ms, which corresponds to about 400 pulses.
• This short ultrasound exposure time ensures that nano-carbon objects such as NCTS are not damaged, and allows them to disagglomerate without breaking them since the energy involved does not generally exceed 5 Joules.
• the mixture of nano-objects and nano-objects of carbon which has been exposed to ultrasound is then set in motion by the peristaltic pump (12) in order to acquire a linear speed which is sufficient for the nano-objects to do not agglomerate again in the pipe (8) after their passage in the reactor and their exposure to ultrasound.
• This linear speed is at least 10 m / min, and can be for example 17 m / min.
• the nano-objects thus arrive via the pipe (8) da ns the high speed tank (1) where they are accelerated and sheared at a shear rate for example 1175 s "1 .
• the na-objects reach locally a velocity of 3 m / s, which guarantees optimal deagglomeration. Below 1 m / s and beyond 5 m / s, there is an agglomeration of na-objects such as NTCs.
• This first step of preparing the aqueous dispersion by combining the ultrasonic mixing technique and the high speed mixing technique generally lasts from 10 to 60 minutes, for example 30 minutes.
• a typical dispersion state of the carbon nanotubes in the dispersion obtained at the end of this first step is represented by the particle size curve of FIG.
• the system is characterized by the presence of agglomerates whose size is for example between 5 ⁇ and 80 ⁇ .
• NTCs are not fully networked, but there are interactions, connections, between these NTCs, and they form surprisingly agglomerates in which they are linked.
• the water expands the network of NTCs but interactions between the NTCs are indeed present.
• the purpose of the first step is not to obtain a perfect dispersion, because then the connections between the tubes no longer exist and one arrives at a statistical state of the dispersion of NTCs.
• the dispersion obtained at the end of the first stage contains, in addition to water, no other solvent and contains no additives, for example of the dispersant type, such as sodium dodecyl sulphate ("Sodium”).
• Dodecyl Sulfate “, SDS) sodium dodecylbenzene sulphate
• Dodecyl Benzene Sulfate “, SDBS lithium dodecyl sulphate
• Lithium Dodecyl Sulfate ", LDS trimethylammonium bromide
• cetiltrimethylammonium bromide cetiltrimethylammonium bromide
• Cetyltrimethyml ammonium bromide CTAB
• Sodium deoxycholate sodium Desoxycholate
• SC sodium taurodeoxycholate
• Telerodeoxycholate DOC
• the dispersion obtained at the end of this first step is constituted by carbon nanotubes and water, usually deionized water.
• This dispersion is a dispersion "out of equilibrium", comprising only a phase of NTCs and non-stable water, it must be kept stirring until the beginning of the second step and not stop the stirring.
• the dispersion In general, during all transfers, the dispersion must always be in motion, always possess kinetic energy, and have a sufficient linear velocity already specified above.
• nano-objects of another material such as silicon particles are mixed with the dispersion consisting of nano-objects of carbon and water obtained during the first time. step using only a high speed mixing technique.
• This second step of the process according to the invention can be implemented with the device represented in FIG. 1 but in which only the high-speed mixing tank equipped with a high-speed stirrer, for example of the Ultra Turrax type. ® is preserved. Ultrasound is not usually desired during this step because they particularly promote the oxidation reaction of silicon with water by producing hydrogen.
• the system operates in a closed loop, ie the hole in the center of the base of the high-speed mixing tank is connected to the pump, which reinjects the solution into the mixing tank. -speed.
• This pump activates the aqueous dispersion of carbon nanotubes and silicon particles from the mixing tank at high speed so that it acquires and maintains a linear velocity that is sufficient for the carbon nanotubes to agglomerate. not again in the pipeline.
• This linear speed can be, for example, 17 m / min in order to avoid reagglomeration and the local rearrangement corresponding to a flow rate greater than 0.5 l / min.
• the high-speed mixing conditions have already been mentioned above, it is a shear rate, for example 1175 s -1 , with a fluid propelled at a "high" speed of 1 m / s to 5 m / sec. s, for example 3 m / s.
• the amount of silicon particles is such that the dispersion of carbon nanotubes and silicon particles obtained generally contains from 5 to 15 g, for example 9 g of silicon particles / L of dispersion.
• the self-assembly is generally no longer possible because the number of silicon particles is too large compared to the number of carbon nanotubes. It is the same below 5 g of silicon particles / L of dispersion.
• the ratio of the number of silicon particles / number of carbon nanotubes should generally not be greater than 1/100. This value of 1/100 is generally the upper limit beyond which it is no longer possible to obtain the desired grape cluster structure.
• the silicon particles are generally added at a constant rate, generally at 10 to 500 mg / min, for example at 300 mg / min. Thus, if 9 g of silicon is added, the duration of the addition will generally be 30 minutes.
• the silicon particles are generally submicron particles, ie whose size such that the diameter is less than 1 ⁇ , for example from 50 nm to 800 nm, for example still 310 nm.
• a spherical shape of the silicon particles is recommended to allow easy insertion of these silicon particles into the entanglement network of carbon nanotubes.
• a silicon powder which is particularly suitable for use in the process according to the invention is a submicron spherical silicon powder, the particles of which have a diameter of about 310 nm and which is available from S'tile (FIG. 3).
• the last "bundles" of carbon nanotubes are abraded and the most entangled carbon nanotubes are extracted by the high speed used and the implementation of a submicron silicon powder that can infiltrate the entanglement network of carbon nanotubes.
• the duration of this step during which the above-mentioned conditions are maintained, namely among others, the addition of the silicon particles at a constant speed, the shear rate, and the high speed of the fluid is generally from 15 to 60.degree. minutes, for example 30 minutes.
• the aqueous dispersion of carbon nanotubes and silicon particles obtained is trimodal and has the particle size characteristics shown in FIG. 4, on which the existence of 3 populations.
• the first population between 100 nm and 700 nm, consists mainly of individual particles of silicon.
• the second population between 5 ⁇ and 60 ⁇ , consists of inflated NTCs constituting macro-agglomerates.
• the third population between 700 nm and 5 ⁇ , consists of a mixture of individual NTCs and micro-agglomerates.
• the third step of the process according to the invention consists in adding at constant speed and in progressively dissolving macromolecules of at least one polysaccharide such as an alginate in the dispersion consisting of carbon nanotubes, silicon particles, and water. and then mixing the macromolecules with the dispersion using a high speed mixing technique.
• polysaccharide macromolecule there is no limitation on the polysaccharide macromolecule and all molecules belonging to the family of polysaccharides can be used in the process according to the invention. It can be natural or synthetic polysaccharides.
• the polysaccharide macromolecule may be selected from pectins, alginates, alginic acid, and carrageenans.
• alginates alginic acid as well as salts and derivatives thereof such as sodium alginate.
• Alginates and especially sodium alginate are extracted from various brown seaweed Phaeophyceae, mainly Laminaria such as Laminaria hyperborea; and Macrocystis such as Macrocystis pyrifera.
• Sodium alginate is the most common commercialized form of alginic acid.
• Alginic acid is a natural polymer of the empirical formula (C 6 H 7 NaO 6 ) n consisting of two monosaccharide units: D-mannuronic acid (M) and L-guluronic acid (G).
• the number of base units of the alginates is generally about 200.
• the proportion of mannuronic acid and guluronic acid varies from one species of seaweed to another and the number of units M on the number of units G can range from 0.5 to 1.5, preferably from 1 to 1.5.
• Alginates are linear unbranched polymers and are not generally random copolymers but according to the alga from which they originate, they consist of sequences of similar or alternating units, namely sequences
• the M / G ratio of alginate from Macrocystis pyrifera is about 1.6 while the M / G ratio of alginate from Laminaria hyperborea is about 0.45.
• the alginates polysaccharides derived from Laminaria hyperborea mention may be made of Satialgine SG 500, among the alginates polysaccharides derived from Macrocystiis pyrifera of different lengths of molecule, mention may be made of the polysaccharides designated A7128, A2033 and A2158 which are generics of acids alginic.
• the polysaccharide macromolecule used according to the invention generally has a molecular weight of 80000 g / mol to 500000 g / mol, preferably 80000 g / mol to 450000 g / mol.
• the amount of polysaccharide added is such that the dispersion obtained generally contains from 1 g to 6 g of polysaccharide / L of dispersion.
• polysaccharide such as an alginate is no longer used for self-assembly but only to the coating of the nanostructure bunch of grapes.
• the polysaccharide is generally added at a constant rate, generally at 10 to 500 mg / min, for example at 100 mg / min.
• a vibrating belt can be used so as to perfectly control the amount and distribution of the polysaccharide particles, for example particles of alginate powder added to the dispersion.
• Dissolution of the polysaccharide, such as alginate, is then progressively, without an agglomeration of these particles of polysaccharide in contact with water.
• This progressive dissolution makes it possible, in a controlled manner, to obtain the self-assembly according to the invention known as "grape bunch", of silicon particles on the backbone of carbon nanotubes.
• the carbon nanotubes are bound and maintained by the polysaccharide such as alginate and thus form a skeleton or three-dimensional network of NTCs.
• the silicon nanoparticles are bonded to the alginate via hydrogen bonds, and the silicon nanoparticles are bonded to the NTC skeleton thanks to the alginate.
• FIG. 5 shows the characteristic granulometric curves of the dispersions of carbon nanotubes and "grape bunch” silicon particles to which alginate has been added, obtained at the end of the third step of the process according to the invention.
• Figure 5 shows that the NTCs have generally disappeared in the structure. Indeed, there is more than a residual peak low at 10 ⁇ corresponding to residues of CNT agglomerates.
• the dispersion is then lyophilized, that is to say that it is successively frozen solidified, then sublimated.
• the dispersion can be poured drop by drop directly into the liquid nitrogen to obtain frozen macro-objects or capsules preferably having a spherical shape and whose size, such as the diameter is for example 5 mm to 20 mm. .
• the size of the manufactured macro-objects has little importance on the internal organization of the grape bunch nanostructure.
• the size of the macro-objects influences only the speed and the quality of freeze-drying.
• This solidification, freezing is in fact the first part of the lyophilization treatment.
• the macro-objects, frozen capsules may be optionally stored in a freezer before proceeding to sublimation and possible subsequent treatments.
• This solidification, freezing the dispersion to give macroobjects, is followed by a sublimation step which constitutes the second part of the lyophilization treatment.
• the frozen solvent namely ice
• Lyophilization is generally carried out under a high vacuum, namely under a pressure not exceeding 5.10 "3 mbar, for example a pressure of 10 " 3 to 10 "7 mbar and at a temperature not exceeding -20 ° C, for example a temperature of -80 ° C.
• the duration of lyophilization depends on the equipment used and can range, for example, from 1 h to 12 h per liter of dispersion.
• the lyophilization treatment may comprise a third part during which the agglomerates are cold-dried.
• this lyophilization step can be carried out even if the first solvent does not comprise a polymer or monomer and / or if the gelled agglomerates are not impregnated in a third step with a particularly water-soluble polymer or monomer.
• Freeze-drying can be carried out whatever the solvent of the gelled agglomerates, whether it be water or any other solvent or mixture of solvents.
• the solvent of the gelled agglomerates contains predominantly water.
• the water content of the macro-objects, lyophilized capsules is generally less than 0.01% by mass.
• the specific organization in "grape bunch" of nano-objects, such as CNTs and silicon nanoparticles, which had been obtained in the dispersion of nano-objects is preserved in the macro-objects, freeze-dried capsules, as it is shown in Figures 6, 7, 8, and 9 where it is observed that silicon nanoparticles are aggregated, self-assembled around a network of NTCs.
• the macro-objects, freeze-dried capsules are constituted by an expanded powder whose grains are loosely assembled and thus form said macro-objects or capsules.
• the self-assembled grape bunch powder thus prepared after lyophilization, is ready for use for any subsequent use, for example to make an ink and does not require grinding that would break the entire organization present in the powder.
• the particle size of the self-assembled grape bunch powder is generally between 1 ⁇ and 100 ⁇ , its specific surface area is generally between 10 m 2 / g and 50 m 2 / g, and its density is generally between 2.014 g / cm 3 and 2,225 g / cm 3 .
• the lyophilized macro-objects can then be mixed, for example by simple mechanical action with all kinds of materials.
• This mechanical action may include one or more operations for example, it can only perform an extrusion; or a simple mechanical mixing can be achieved; or we can achieve a simple mechanical mixing optionally followed by drying of the mixture.
• the specific organization according to the invention, in grape bunch, of nano-carbon objects and nano-objects made of another material, such as CNTs and silicon nanoparticles, is preserved after this mechanical action.
• vehicle of an ink or paste is generally meant components, ingredients necessary to communicate to this ink or paste and the marking obtained with this ink or paste the desired properties.
• the vehicle of the ink or paste generally comprises a binder and a solvent.
• the vehicle may further comprise at least one electronic conductor different from the composite material according to the invention.
• the ink in which the composite material according to the invention can be incorporated there is no limitation on the ink in which the composite material according to the invention can be incorporated, in particular there is no limitation with regard to the vehicle, the binder and the solvent with which the material according to the invention can be mixed to prepare an ink or paste.
• the ink may be a water-based ink, that is to say one whose solvent mainly comprises water or consists of water; an organic-based ink, that is to say one whose solvent mainly comprises one or more organic solvents or is constituted by one or more organic solvents, for example a so-called fat-based ink whose solvent is constituted by one or more drying oils; an ink based on a sol-gel of silica or carbon.
• the binder may be chosen from organic polymers such as photo-crosslinkable polymers such as acrylic polymers, heliographic resins, photolithographic resins, crosslinkable thermosetting polymers such as epoxides, natural polymers such as the polysaccharides already mentioned above. like alginates.
• organic polymers such as photo-crosslinkable polymers such as acrylic polymers, heliographic resins, photolithographic resins, crosslinkable thermosetting polymers such as epoxides, natural polymers such as the polysaccharides already mentioned above. like alginates.
• the solvent is water
• the binder is a polysaccharide such as an alginate. More preferably, the binder is the same polysaccharide as that of the nanocomposite material according to the invention.
• This ink or paste is generally intended for the preparation of an electrode by coating, printing, depositing, using a printing device, said ink or paste on a current collector.
• the composite material according to the invention in which the polysaccharide has been carbonized and converted into amorphous carbon can be used as an electrochemically active electrode material in any electrochemical system.
• the composite material prepared according to the invention can in particular be used after carbonization and conversion of the polysaccharide to amorphous carbon, as electrochemically active material of positive or negative electrode in any electrochemical system, in particular in any non electrolyte electrochemical system. aqueous.
• This positive or negative electrode comprises, besides the electrochemically active material of positive or negative electrode as defined above, a binder which is generally an organic polymer, optionally one or more additive (s) conductor (s) electronic (s), and a current collector.
• a binder which is generally an organic polymer, optionally one or more additive (s) conductor (s) electronic (s), and a current collector.
• the organic polymer may also be chosen from polytretrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) and the PVDF-HFP copolymer (propylene hexafluoride); carboxymethylcellulose; and elastomers such as CMC-SBR (carboxymethylcellulose-rubber styrene butadiene).
• PTFE polytretrafluoroethylene
• PVDF polyvinylidene fluoride
• PVDF-HFP copolymer propylene hexafluoride
• carboxymethylcellulose elastomers
• CMC-SBR carboxymethylcellulose-rubber styrene butadiene
• the binder is a polysaccharide such as an alginate.
• the binder is the same polysaccharide, such as an alginate, than that of the nanocomposite material according to the invention.
• the optional electronic conductive additive may be chosen from metal particles such as Ag particles, graphite, graphene, carbon black, carbon fibers, carbon nanowires, carbon nanotubes, and polymers. electronic conductors, and their mixtures.
• graphene and carbon fibers can fulfill exactly the same role as graphite in ink.
• the current collector is generally in the form of a sheet of copper, nickel or aluminum.
• the electrode generally comprises from 70% to 94% by weight of electrochemically active material, from 1% to 20% by weight, preferably from 1% to 10% by weight of the binder, and optionally from 1% to 15% by weight. the electronic conductive additive (s).
• Such an electrode can be prepared in a conventional manner by forming, as described above, a suspension, paste or ink with the composite material according to the invention, the binder, optionally the additive (s) conducting (s) and a solvent depositing, coating or printing this suspension, paste or ink on a current collector, drying the ink, deposited paste or suspension, calendering, squeezing the ink or paste deposited, dried and the current collector, and finally heat treating the electrode to carbonize the polysaccharide, such as an alginate, and transform it into amorphous carbon.
• the binder optionally the additive (s) conducting (s) and a solvent depositing, coating or printing this suspension, paste or ink on a current collector, drying the ink, deposited paste or suspension, calendering, squeezing the ink or paste deposited, dried and the current collector, and finally heat treating the electrode to carbonize the polysaccharide, such as an alginate, and transform it into amorphous carbon.
• the material according to the invention is incorporated in the ink vehicle, that is to say a mixture of binder, solvent, and optional conductive additives.
• the solvent and the binder are in the form of an aqueous polysaccharide gel, such as an alginate hydrogel.
• an aqueous polysaccharide gel such as an alginate hydrogel.
• the incorporation of the material according to the invention into this mixture is preferably carried out by a mixing technique without grinding, in a mixing apparatus causing no grinding, and involving a very low energy, namely generally less than 100. Joules / tower, to preserve the self-assembly of carbon nanotubes with silicon nanoparticles that is preserved at 60 J / revolution.
• Such a mixing apparatus makes it possible to avoid lumps, and makes it possible to retain an ink fineness of less than 10 ⁇ .
• the ink, paste or suspension can be applied by any suitable method such as coating, coating, gravure, flexography, offset.
• the thickness of ink, paste, or deposited suspension, applied is generally 50 to 300 ⁇ , for example 100 ⁇ .
• the deposited ink, paste, or suspension is generally dried at room temperature, namely 15 ° C to 30 ° C, preferably 20 ° C.
• the heat treatment of the electrode in order to carbonize the polysaccharide, such as an alginate, and to transform it into amorphous carbon is generally carried out at a temperature of 400 ° C. to 650 ° C., for example 600 ° C., for a period of time. from 15 to 60 minutes, for example 30 minutes under a sweep of inert gas such as argon or under a slightly reducing gas sweep, such as a mixture of an inert gas such as argon and a reducing gas as hydrogen, by a mixture of argon and hydrogen (for example 2% by volume of hydrogen).
• inert gas such as argon
• a slightly reducing gas sweep such as a mixture of an inert gas such as argon and a reducing gas as hydrogen
• Electrodes are then cut into pellets and these pellets can then be treated with a hydrogen plasma to deoxidize the silicon when the composite material comprises and etch the amorphous carbon to improve the accessibility of the electrolyte to the surfaces of the nanoparticles. silicon.
• the electrochemical system in which the electrode according to the invention is implemented can be in particular a rechargeable electrochemical accumulator with non-aqueous electrolyte such as an accumulator or a lithium battery, and more particularly a lithium ion accumulator, which in addition to the positive or negative electrode as defined above, comprising as electrochemically active material the composite material prepared according to the invention in which the polysaccharide has been carbonized and converted into amorphous carbon, comprises a negative or positive electrode which does not include the composite material according to the invention, and a non-aqueous electrolyte.
• a rechargeable electrochemical accumulator with non-aqueous electrolyte such as an accumulator or a lithium battery
• a lithium ion accumulator which in addition to the positive or negative electrode as defined above, comprising as electrochemically active material the composite material prepared according to the invention in which the polysaccharide has been carbonized and converted into amorphous carbon, comprises a negative or positive electrode which does not include the composite material according to the
• the negative or positive electrode which does not comprise as an electrochemically active material the composite material according to the invention in which the polysaccharide has been carbonized, comprises an electrochemically active material different from the composite material according to the invention, a binder, optionally one or more electronic conductive additive (s) and a current collector.
• the electrochemically active material of the negative or positive electrode which does not comprise the composite material according to the invention in which the polysaccharide has It has been carbonized as an electrochemically active material and can be selected from any material known to those skilled in the art.
• the electrochemically active material of the negative electrode when the composite material according to the invention in which the polysaccharide has been carbonized is the electrochemically active material of the negative electrode, then the electrochemically active material of the positive electrode may be chosen from lithium metal and any material known to the skilled person in this field of the art.
• the electrochemically active material of the positive electrode is formed by the material according to the invention in which the polysaccharide has been carbonized
• the electrochemically active material of the negative electrode can be made of any material known and adaptable by the human being. job.
• the electrolyte may be solid or liquid.
• the electrolyte When the electrolyte is liquid, it consists for example of a solution of at least one conductive salt such as a lithium salt in an organic solvent and / or an ionic liquid.
• the electrolyte When the electrolyte is solid, it comprises a polymeric material and a lithium salt.
• the lithium salt may be chosen for example from LiAsF 6 , LiClO 4 , LiBF 4 , LiPF 6 , LiBOB, LiODBF, LiB (C 6 H 5 ), LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 (LiTFSI) , LiC (CF 3 SO 2 ) 3 (LiTFSM).
• the organic solvent is preferably a solvent compatible with the constituents of the electrodes, relatively nonvolatile, aprotic and relatively polar.
• ethers, esters and mixtures thereof may be mentioned.
• the ethers are chosen in particular from linear carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), methylethyl carbonate (EMC), dipropyl carbonate (DPC), cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), and butylene carbonate; alkyl esters such as formates, acetates, propionates and butyrates; gamma butyrolactone, triglyme, tetraglyme, lactone, dimethylsulfoxide, dioxolane, sulfolane and mixtures thereof.
• the solvents are preferably mixtures including EC / DMC, EC / DEC, EC / DPC and EC / DMC.
• the accumulator may have the shape of a button cell.
• the stainless steel shims (104) which serve both for example to cut the lithium metal and, later, to ensure good contact of the current collectors with the external parts of the battery,
• a silicon nanoparticle / carbon nanotube composite material according to the invention is prepared by the process according to the invention as described above.
• This composite material is in the form of a self-assembled powder having the grape bunch structure characteristic of the material according to the invention.
• the nanotubes are Graphistrenght ° brand nanotubes available from ARKEMA °. These are multiwall nanotubes with a purity higher than 90%, with a mean diameter between 10 nm and 15 nm, and with an average length of 7 ⁇ .
• the specific surface area of these nanotubes is between 20 m 2 / g and 70 m 2 / g
• the starting granulometry is between 10 ⁇ and 100 ⁇ mainly in the form of entangled nanotubes and forming agglomerated balls.
• the beaker is placed under a high-speed disperser Ultra-Turrax ° type set at 2000 rpm.
• Silicone hoses are then used to connect the beaker to the inlet of an ultrasonic reactor through the first channel of a peristaltic pump (which has 2 channels), and connect the reactor outlet to the beaker via of the second channel of the peristaltic pump.
• the peristaltic pump is set at 200 rpm which amounts to a circulation speed of 0.77 liters / min of NTCs solution.
• the mixing time is 30 minutes.
• the pump and ultrasonic system are stopped, and only high speed agitation is maintained at 2000 rpm.
• Silicon is in the form of a powder available from the company
• the initial particle size is 310 nm.
• the powder consists of substantially spherical particles with small agglomerates of a size between 1 ⁇ and 5 ⁇ .
• the developed surface of the powder is estimated at 14 m 2 / g
• the operation lasts 35 minutes before the dispersion is diluted twice with deionized water, and 6 g of alginate in powder form are added inside the vortex.
• Alginate is commercial alginate manufactured by CI MAPREM °. The grade, quality, used is CI MALGI N * 80/400.
• the particle size of the alginate powder is between 100 ⁇ and
• the frequency of addition is 200 mg / min for 30 minutes.
• the self-assembly in bunches of grapes is done during this stage.
• Draining is performed dropwise in liquid nitrogen.
• the almost instant freezing of drops of solution freezes the organization into a bunch of grapes.
• the self-assembly of the silicon nanoparticles on the network of NTCs is carried out during the lyophilization of the "drops" of ice.
• the freeze-drying conditions are a temperature of -90 ° C. with a vacuum of 0.002 mbar.
• the duration of this operation is 8 hours.
• the electronic conduction and the stiffening of the self-assembly in bunches of grapes is carried out by carbonization of the freeze-dried powder.
• freeze-dried powder is placed in quartz crucibles, and two primary vacuum cycles are carried out in a horizontal furnace, with successive fillings of 2% hydrogenated argon.
• the temperature cycle is a rise in temperature from room temperature to 600 ° C at a rate of 20 ° C / min, followed by a plateau at 600 ° C for one hour.
• a negative electrode is prepared with the composite material according to the invention prepared in Example 1.
• the first step is to prepare an ink comprising 1.5 g of the composite material according to the invention prepared in example 1 and a vehicle composed of 1.875 g of an aqueous 8% alginate hydrogel corresponding to 0.15 g of alginate.
• Alginate is a commercial product of the company CI MAPREM ° reference CIMALGI N500 *.
• the alginate gel is obtained by extrusion in a twin-screw extruder (Prism extruder) of 100 g of alginate with 1250 g of water. Such an extrusion process has been retained because it makes it possible to maximize the entanglements.
• Example 1 1.5 g of the self-assembled powder prepared in Example 1 are incorporated in 1.875 g of the alginate gel previously prepared by extrusion (92% water and 8% by weight of alginate previously extruded), in order to prepare a ink.
• the incorporation of the powder in the alginate gel is carried out by a mixing technique without grinding, in a mixing apparatus thus causing no grinding.
• this incorporation operation is not a grinding operation, because the energy involved is very low, ie less than 125 J / turn to preserve the nanostructure constituted by the self-assembly of the nanotubes of carbon with silicon nanoparticles at a scale less than 10 ⁇ .
• the mixing device used makes it possible to avoid lumps, and makes it possible to retain an ink fineness of less than 10 ⁇ .
• the VGCF ° carbon fibers manufactured by the company SHOWA DEN KO have diameters of 150 nm with lengths between 10 ⁇ and 20 ⁇ .
• the electrical resistivity of these fibers is 10 "4 ⁇ .cm
• VGCF ° carbon fibers are used here as an electronic conductor in addition to carbon nanotubes. Indeed if within each cluster size less than 10 ⁇ , there is already an intrinsic electronic conductivity due to NTCs, it is necessary to create long-distance electronic conductivity, namely beyond 10 ⁇ , between each cluster.
• the VGCF ° carbon fibers are used to electronically connect the cluster structure and provide a long-distance conductivity of 10 "4 ⁇ .cm.
• This ink is then coated on a copper current collector to a thickness of 100 ⁇ with a basis weight of 2 mg / cm 2 and dried at room temperature thus forming an electrode.
• the current collector coated with the dried ink layer is then heat-treated at 600 ° C for 30 minutes under a hydrogenated argon sweep (2%) to convert the alginate to amorphous carbon.
• the loss of mass does not exceed 30%, which is a low value which guarantees a good cohesion of the electrode and a good adhesion to the copper strip.
• the electrode is then cut into pellets 16 mm in diameter and
• Figures 12 and 13 show the structure of the pellets after the plasma treatment.
• FIG. 17 also shows the structure of the electrode according to the invention in which the carbon nanotubes and the silicon nanoparticles have an organization in bunches of grapes.
• the negative electrode prepared in Example 2 is tested in a lithium-metal battery (half-battery test) of the button cell type. Each button cell is mounted carefully respecting the same protocol.
• a negative electrode according to the invention (16 mm in diameter, 100 ⁇ in thickness) (101) deposited on a copper disk serving as a current collector 50 ⁇ thick;
• the electrolyte impregnates a separator which is a microporous membrane of polyolefin, more specifically a microporous polypropylene membrane Celgard ° (102) 0 16.5 mm;
• a positive electrode (103) consisting of a disk of 14 mm diameter lithium metal
• the stainless steel case is then closed with a crimper, making it perfectly airtight.
• the button cell Due to the high reactivity of lithium and its salts with oxygen and water, the button cell is put in a glove box. This is maintained in slight overpressure under anhydrous argon atmosphere. Sensors provide continuous monitoring of oxygen and water concentrations. Typically, these concentrations should remain below the ppm.
• the button cell prepared according to the procedure described above is cycled, i.e. charges and discharges at different constant current regimes, for a specified number of cycles, to evaluate the practical capacity of the battery. .
• a battery that charges at C / 20 is a battery which is imposed a constant current for 20 hours in order to recover its full capacity C.
• the current value is equal to the capacity C divided by the number of hours of charging ie in this case 20 hours.
• the capacity is 8.5 mAh.
• a negative electrode is tested, prepared with a material prepared from a statistical dispersion of carbon nanotubes and silicon nanoparticles.
• Carbon nanotubes are commercially available nanotubes, available from Arkema under the name Graphistrenght °.
• These nanotubes are multiwall nanotubes with a purity higher than 90%, with a mean diameter of between 10 nm and 15 nm, and with an average length of 7 ⁇ .
• the specific surface area of these nanotubes is between 20 m 2 / g and 70 m 2 / g.
• the starting granulometry is between 10 ⁇ and 100 ⁇ , mainly in the form of entangled nanotubes and forming agglomerated pellets.
• the initial particle size is 310 nm and consists of substantially spherical particles with small agglomerates of a size between 1 ⁇ and 5 ⁇ .
• the developed surface is estimated at 14 m 2 / g
• the statistical mixture between the NTCs and the silicon is carried out by ultrasound and lasts 30 minutes.
• VGCF ° carbon fibers which come from SHOWA DENKO. These VGCF ® carbon fibers have diameters of 150 nm and lengths between 10 ⁇ and 20 ⁇ .
• the electrical resistivity is 10 "4 ⁇ .cm.
• the ink is mixed with the Ultra-Turrax® high-speed mixer at a rotation speed of 2000 rpm for 15 minutes.
• the electrode thus prepared is then punched to a diameter of 14 mm before being mounted in a lithium-metal battery (test half-stack) button cell type prepared as in Example 3.
• Figure 16 shows the structure of this electrode according to the prior art prepared from a statistical dispersion of carbon nanotubes and silicon nanoparticles and which therefore does not have the grape bunch structure according to the invention.

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