EP2356070A1 - PROCEDE DE FABRICATION D'UN MATERIAU COMPOSITE SnO2 ET NANOTUBES DE CARBONE ET/OU NANOFIBRES DE CARBONE, MATERIAU OBTENU PAR LE PROCEDE, ELECTRODE POUR BATTERIE AU LITHIUM COMPORTANT LEDIT MATERIAU - Google Patents
PROCEDE DE FABRICATION D'UN MATERIAU COMPOSITE SnO2 ET NANOTUBES DE CARBONE ET/OU NANOFIBRES DE CARBONE, MATERIAU OBTENU PAR LE PROCEDE, ELECTRODE POUR BATTERIE AU LITHIUM COMPORTANT LEDIT MATERIAUInfo
- Publication number
- EP2356070A1 EP2356070A1 EP09803810A EP09803810A EP2356070A1 EP 2356070 A1 EP2356070 A1 EP 2356070A1 EP 09803810 A EP09803810 A EP 09803810A EP 09803810 A EP09803810 A EP 09803810A EP 2356070 A1 EP2356070 A1 EP 2356070A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composite material
- carbon
- manufacturing
- carbon nanotubes
- fibrillar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 17
- 239000002041 carbon nanotube Substances 0.000 title claims description 47
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims description 38
- 239000000463 material Substances 0.000 title claims description 27
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims 2
- 229910052744 lithium Inorganic materials 0.000 title description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 30
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 29
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- 230000006911 nucleation Effects 0.000 claims abstract description 13
- 238000010899 nucleation Methods 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002134 carbon nanofiber Substances 0.000 claims description 17
- 230000001351 cycling effect Effects 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 230000002441 reversible effect Effects 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 238000000498 ball milling Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000002071 nanotube Substances 0.000 abstract description 19
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 abstract description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 20
- 239000012071 phase Substances 0.000 description 11
- 239000002109 single walled nanotube Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 6
- 239000004917 carbon fiber Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000002121 nanofiber Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- -1 silicon Chemical compound 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 101100317222 Borrelia hermsii vsp3 gene Proteins 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012984 LiVLi Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- AOVKLNZJIJAUBS-UHFFFAOYSA-N [C].[O].[Sn] Chemical class [C].[O].[Sn] AOVKLNZJIJAUBS-UHFFFAOYSA-N 0.000 description 1
- QWJYDTCSUDMGSU-UHFFFAOYSA-N [Sn].[C] Chemical compound [Sn].[C] QWJYDTCSUDMGSU-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/17—Purification
-
- 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
- H01M4/36—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
- H01M4/58—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
-
- 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 method for manufacturing a composite material comprising a fibrous carbon material and tin oxide.
- fibrillar carbon material By fibrillar carbon material, one understands the carbon nanotubes NTC or the nanofibers of carbon NFC or a mixture of both.
- the invention also relates to electrodes made of said material and lithium batteries comprising such electrodes.
- the invention applies to the field of storage of electrical energy in batteries and more particularly in lithium secondary batteries Li-ion type.
- Tin like silicon, is likely to form alloys with lithium and allow to obtain capacities much higher than those achieved with graphite.
- Japan the world's largest producer, alone produced more than 1200 million lithium-ion batteries per year (ITE EXPRESS News, (2005).
- Li-ion batteries SnO 2, SnO 2, SnO 2, .
- These materials have a capacity much greater than that of graphite carbon, but their lifetime is very limited because volume change during cycling during the alloy reaction.
- several ideas have been put forward, such as the use of nanoscale particles or the development of carbon-tin or carbon-tin oxide composites.
- J. Xie et al published an article entitled: "Synthesis and
- the initial discharge capacity is 600 mAh / g, which shows that there is a strong irreversibility at the start.
- the synthesis method used consists of treating at high temperature (600 ° C.) the NTC-SnO 2 mixtures obtained by impregnating two types of CNTs (open-end CNTs and closed-ends CNTs) in an acid solution of tin. (SnCl 2 + HCI).
- the discharge capacity obtained for the open-end CNT-based composite is less than 600 mAh / g.
- document D1 relates to a process for depositing tin oxide particles on carbon fibers. It does not describe a process for depositing tin oxide on carbon nanofibers, or on carbon nanotubes.
- the carbon fibers have a diameter of about 10 micrometers.
- the SnO2 layer deposited on the surface of a fiber, according to this document, preferably has a thickness of 250 nm.
- the carbonaceous material consists of NTC or NFC or a mixture of NTC and NFC.
- the diameters of the CNTs and NFCs are not comparable to those of the fibers described in D1 since they are nanometers and not micrometers. In fact, for single-wall CNTs, at most a diameter of 2.2-2.3 nm is reached. Multi-wall CNTs have an external diameter ranging from 3 to 50 nm and NFCs have diameters of 50 to 200 nm.
- multi-walled NTCs of external diameter ranging from 3 to 50 nm, preferably from 5 to 30 nm and better still from 8 to 20 nm, are preferably used.
- the process described in D1 comprises a dissolving operation done with stirring at a temperature of 40 ° C. and not at room temperature as in the present invention. The pressure under which this step is made is not given.
- This process involves a precipitation with ammonia, which corresponds to a chemical precipitation / nucleation.
- the method comprises a nucleation / crystallization phase which is a physical step since it corresponds to a drying step and then a heat treatment step.
- the drying step causes evaporation of the reaction medium (ie water) and thus, physical precipitation.
- the reaction medium ie water
- One of the advantages of this physical nucleation step is its ease of industrial implementation (use of a simple evaporator or oven) and its non-production of liquid effluent (apart from the water of the reaction medium); which industrially is interesting because it leads to less effluent reprocessing.
- the problem solved is the production of a composite material comprising a fibrous carbonaceous material (NTC and / or NFC) and tin oxide having good electronic conductivity, a moderate volume expansion during electrochemical cycling. and also a good reversible ability.
- the composite material has galvanostatic cycling, a capacity greater than 600 mAh / g after 60 cycles for the realization of electrodes.
- - D2 is a June 2, 2008 publication of Yu-Jin CHEN et al titled "High Capacity and Excellent Cycling Stability of Single-Walled Carbon Nanotubes / SnO2 Core-shell Structures as Li-insertion Matehal".
- the composite material described in this document consists of single wall nanotubes (SWNTs) and SnO2.
- Document D2 specifies that the initial discharge capacity of the "core-shell" structures is greater than 1399 mAh / g and that the reversible capacities of these structures are stabilized at about 900 mAh / g after 100 cycles.
- the document also states that the diameter of the tin particles deposited on the surface of the nanotubes is about 2 nm and that the length of the single wall carbon nanotubes (SWNTs) is about 20 microns.
- SWNTs / SnO2 structures have a very large surface and a very long length / diameter ratio leading to their large capacity. Indeed, in this case, the reversible capacitance of the core-shell structures of nanotubes coated with tin oxide is high.
- the nanotubes are then rinsed with distilled water. 1 g of tin chloride is placed in a container containing 40 ml of distilled water and then 0.7 ml of 38% hydrochloric acid is added. 10mg of previously cleaned mono-walled carbon nanotubes are put into the prepared solution. Ultrasound is applied to the solution for 3 to 5 minutes and then stirred for 30 to 60 minutes at room temperature.
- nanotubes thus treated are rinsed with distilled water. Then these carbon nanotubes covered with tin oxide are filtered.
- the process described in D3 comprises a step of filtering the nanotubes coated with tin oxide. Filtration is an operation which results in loss of tin, so the method described therein has a lower tin yield than that of the present invention.
- the Applicant has reproduced the experimental conditions described in this document.
- the curve of discharge capacity as a function of the number of cycles, obtained under these conditions, is illustrated in FIG. 4 and shows that at the end of the second cycle the capacity drops to 790 mAh / g and that after 12 cycles this capacity drops to 620mAh / g.
- the capacity is greater than 800 mAh / g after 12 cycles.
- the poor tin yield has been confirmed, this yield being 1, 1%, the process used using a large amount of tin.
- the problem which the Applicant has sought to solve by the present invention is to propose a method of manufacturing a composite material comprising a fibrillar carbon material and tin oxide without the disadvantages of the deposition processes which have just been described.
- the fibrillar carbon / tin oxide composites thus produced according to the present invention have a good electronic conductivity, a moderate volume expansion during the electrochemical cycling and also a good reversible capacity.
- the Applicant proposes a method which makes it possible to control the effects of volume expansion during cycling so as not to cause excessive performance losses.
- the proposed method is simple to implement because it uses low temperature conditions and atmospheric pressure for the attachment of tin oxide particles on the surfaces of the carbonaceous fibrillar material.
- This method is more efficient than the solutions known to date because the composite material obtained has a capacity in charge and discharge after several cycles, greater than that of composite materials in carbon nanotubes and tin oxide of the state of the technical.
- the method does not use any technique likely to deteriorate the performance of the fibrillar carbon material used as is the case in the techniques using ultrasound.
- the method makes it possible to use a fibrous carbon material such as carbon nanotubes but also carbon nanofibers or a mixture of carbon nanotubes and nanofibers.
- the present invention more particularly relates to a method of manufacturing a composite material comprising tin oxide particles and a fibrillated carbonaceous material, mainly characterized in that it comprises a synthesis by precipitation / nucleation in a water-alcohol medium of tin hydroxide particles derived from a tin salt, in the presence of the fibrillar carbonaceous material and of an acid, in that the fibrous carbonaceous material consists of carbon nanotubes or carbon nanofibers or a mixture of carbon nanotubes and carbon nanofibers and in that the synthesis comprises a dissolution / contact phase , carried out at ambient temperature and at atmospheric pressure, then a nucleation / chstallization phase carried out at a temperature above ambient temperature and finally a heat treatment phase.
- tin salt is dissolved in a mixture of water, alcohol and acid and stirred, water is added while stirring is maintained; b) the fibrous carbonaceous material is added and the mixture is stirred, whereby steps a) and b) can be carried out in this order or in the reverse order.
- the nucleation / crystallization phase comprises dry evaporation.
- the drying consists in fact in bringing the reaction mixture to a temperature higher than the ambient temperature (typically 25 ° C under 1atms) but lower than the boiling temperature of the mixture (typically less than 100 0 C).
- This dry evaporation is, for example, carried out at a temperature of between 25 and 80 ° C., or better still of 40 ° C. at 70 ° C.
- the heat treatment phase consists of heating the product obtained at a temperature much higher than the boiling temperature of the reaction mixture. This heat treatment phase is carried out in an oven, under nitrogen or in air, for about ten minutes, at a temperature of between 300 ° and 500 ° C.
- Drying ensures nucleation while heat treatment provides crystallization.
- Nucleation is carried out according to the invention by a physical step.
- the fibrillar carbonaceous material may be added during the dissolving / contacting phase in powder form or in pre-dispersion.
- Previous predispersion can be achieved by milling in planetary ball mill type water or the like.
- the agitation is vigorous stirring, which may be identical to that practiced in the case of predispersion. This energetic agitation breaks down the aggregates and increases the density of the material. In other cases of agitation, stirring can be carried out by means of a blade (non-energetic agitation).
- the fibrous carbonaceous material consists of carbon nanotubes or carbon nanofibers or a mixture of carbon nanotubes and carbon nanofibers.
- carbon nanotubes is meant hollow tubes with one or more graphitic plane walls, concentric from 2 to 50 nm in outer diameter.
- carbon nanofibers is meant solid fibers of graphitic carbon, with a diameter of 50 to 200 nm, but which may often have a thin hollow central channel.
- the length / diameter ratio is much greater than 1, typically greater than 100.
- the Applicant has found that it is preferable to obtain the best results of treating the fibrillar carbon material at the output of manufacture (synthesis). This material is treated so as to remove the catalytic residues present. Thus, the tin oxide particles adhere better to the surfaces.
- This purification treatment consists of carrying out an oxidation which enables the fibrillar carbonaceous material to exhibit OH and / or COOH type surface polar functions.
- the purification is obtained for example by means of a strong mineral acid such as HNO 3 or H 2 SO 4 .
- the acid treatment is followed by a surface oxidation operation by means of sodium hypochlorite (NaOCl) or hydrogen peroxide (H2O2) or ozone (O 3), when the selected acid to purify is not enough oxidizing (for example H 2 SO 4 ).
- the invention also relates to the composite material obtained by the process as described, the material being mainly characterized in that it consists of a homogeneous distribution of tin particles on the surfaces of the fibrillar carbonaceous material with a virtual absence of tin particles not supported by said material.
- the material consists of 20 to 35% by weight of fibrous carbonaceous material and 65 to 80% by weight of tin oxide particles.
- the fibrous carbonaceous material is a mixture of carbon nanotubes and carbon nanofibers
- this mixture is preferably composed of 50% by weight of each of the two constituents.
- the composite material described consists of carbon nanotubes and tin oxide particles, it has galvanostatic cycling, a capacity greater than 600 mAh / g after 60 cycles.
- the composite material consists of carbon nanotubes, carbon nanofibers and tin oxide particles, it has, in galvanostatic cycling, a capacity greater than 750 mAh / g after 60 cycles.
- the carbon nanotubes are preferably multi-wall CNTs.
- an electrode comprises a composite material consisting of a mixture of at least 80% by weight of active material (NTC-SnO 2) and at most 20% by weight of binder.
- the binder can consist of any liquid, or molecular or polymeric paste, chemically inert, generally used to adhere together powder particles, such as polyvinylidenedifluoride (PVDF), polyvinylpyrrolidone (PVP), CMC (carboxymethylcellulose) .
- PVDF polyvinylidenedifluoride
- PVP polyvinylpyrrolidone
- CMC carbboxymethylcellulose
- the invention applies to the production of lithium-ion batteries comprising a negative electrode comprising a composite material as described above. Brief description of the drawings
- FIG. 1 represents the load capacitance and discharge curves of a composite material consisting of NTC-SnO 2 as a function of the number of cycles.
- FIG. 2 represents a scanning electron microscope photograph of the composite material according to the invention with a magnification of
- FIG. 3 represents a diagram of an exploded view of an elementary lithium battery cell according to the invention.
- FIG. 4 represents the discharge capacity curve as a function of the number of cycles obtained under the experimental conditions reproduced by FIG.
- purified CNTs are used as fibrous carbonaceous material to obtain better adhesion of the tin particles as previously described.
- the Applicant has found that the carbon nanotubes at the output of synthesis are not adapted to the process.
- the surface of the nanotubes must have surface polar functions of the OH and / or COOH type. These functions are obtained by treating the nanotubes in a strong acid such as HNO3 (oxidizing acid) or H 2 SO 4 (weakly oxidizing acid), followed by surface oxidation by means of sodium hypochlorite if acid used to purify is not enough oxidizing.
- oxidants such as H 2 O 2 or O 3 can also be used without compromising the scope of the invention.
- tin oxide particles of the order of a few nanometers provided better results.
- the particles used are advantageously nanoparticles of tin oxide. This first example is carried out in the following steps:
- the negative electrode A consists of a mixture of 80% by weight of active material (NTC-SnO 2 ) and 20% by weight of PVDF (PolyVinylidene difluoride), which is a binder for ensuring good mechanical strength. of the electrode. These different constituents are introduced into N-methyl pyrrolidone in order to obtain a very homogeneous mixture. This mixture is then coated on a glass plate by "Doctor BLADE" enducous plate.
- the coating is at a thickness of 150 microns. Electrodes 11 mm in diameter are then cut from this film and dried for several hours (6 to 8 hours) at 80 ° C under vacuum.
- the negative electrode A is covered successively with a separator S (polypropylene impregnated electrolyte) and the positive electrode K which is a lithium metal pellet.
- the electrolyte used is a lithium salt (LJPF6, 1M) dissolved in the organic solvent mixture EC / DMC (ethylene carbonate / DiMethyl carbonate) in the proportions by volume 1/1.
- EC / DMC ethylene carbonate / DiMethyl carbonate
- VMP3 Biology SAS
- NTC-SnO2 composites were studied in C / 10 constant mode galvanostatic mode in the potential window [0.02-1.2] V (vs. LiVLi).
- FIG. 1 represents the electrochemical performances in charge-discharge of the carbon nanotube-SnO 2 composite used as negative electrodes (anode) for Li-ion batteries.
- This negative electrode consists of the material synthesized by the process just described.
- the reversible capacity drops at the end of the first cycle but remains at about 700 mAh / g for more than 30 cycles. After 60 cycles, the composite capacity remains above 600mAh / g.
- Figure 2 is an electron microscope view of the NTC-SnO2 composite. In this figure, we can see the homogeneous distribution of tin nanoparticles on the walls of carbon nanotubes and a virtual absence of unsupported particles.
- Example 3
- This example reproduces the test conditions of Example 2 but replacing in the synthesis half of the carbon nanotubes, ie 0.5 g per 0.5 g of carbon nanofibers (for example, it is nanofibers of carbons sold by the company Showa Denko and whose diameter is 150 nm).
- Nanofibers are able to provide electrical connections over long distances and carbon nanotubes act more locally.
- nanotubes seem to play the role of "elastomeric” material to accommodate volumic variations, as well as short-distance electrical connectors between particles and nanofibers seem to play the role of long-distance connector.
- the nanotubes used are purified so that the ash content is less than 2.5% by weight loss at 900 0 C in air and the nature of the surface, because at the output of synthesis, the nanotubes contain catalytic residues which can reach up to 10% by weight.
- the invention presented here makes it possible for a tin oxide SnO 2 to obtain a reversible capacity of the order of 850 mAh / g after 50 cycles without unfavorable volume expansion.
- the composite material obtained by the process (SnO 2 with a fibrillar carbon material) also provides the following results:
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0858459A FR2939786B1 (fr) | 2008-12-11 | 2008-12-11 | Procede de fabrication d'un materiau composite sno2 et nanotubes de carbone et/ou nanofibres de carbone, materiau obtenu par le procede, electrode pour batterie au lithium comportant ledit materiau. |
PCT/FR2009/052408 WO2010066989A1 (fr) | 2008-12-11 | 2009-12-04 | PROCEDE DE FABRICATION D'UN MATERIAU COMPOSITE SnO2 ET NANOTUBES DE CARBONE ET/OU NANOFIBRES DE CARBONE, MATERIAU OBTENU PAR LE PROCEDE, ELECTRODE POUR BATTERIE AU LITHIUM COMPORTANT LEDIT MATERIAU |
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EP2356070A1 true EP2356070A1 (fr) | 2011-08-17 |
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EP09803810A Withdrawn EP2356070A1 (fr) | 2008-12-11 | 2009-12-04 | PROCEDE DE FABRICATION D'UN MATERIAU COMPOSITE SnO2 ET NANOTUBES DE CARBONE ET/OU NANOFIBRES DE CARBONE, MATERIAU OBTENU PAR LE PROCEDE, ELECTRODE POUR BATTERIE AU LITHIUM COMPORTANT LEDIT MATERIAU |
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US (1) | US20110297889A1 (zh) |
EP (1) | EP2356070A1 (zh) |
JP (1) | JP2012511492A (zh) |
KR (1) | KR20110094186A (zh) |
CN (1) | CN102307807A (zh) |
FR (1) | FR2939786B1 (zh) |
WO (1) | WO2010066989A1 (zh) |
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JP2011253620A (ja) * | 2009-09-30 | 2011-12-15 | K & W Ltd | 負極活物質、この負極活物質の製造方法、及びこの負極活物質を用いたリチウムイオン二次電池 |
MX2010013211A (es) * | 2010-12-01 | 2012-06-08 | Urbanizaciones Inmobiliarias Del Ct S A De C V | Material compuesto a base de cascarilla de arroz y aglutinante modificado con nanoestructuras de carbono. |
CN102110807B (zh) * | 2011-01-27 | 2013-06-19 | 东莞市迈科科技有限公司 | 一种氧化锡/碳纳米管复合负极材料的制备方法及该材料的应用 |
CN102208638B (zh) * | 2011-04-26 | 2013-10-23 | 浙江大学 | 高容量锂离子电池负极复合材料及其制备方法 |
CN102646457A (zh) * | 2012-04-28 | 2012-08-22 | 苏州新动能源材料有限公司 | 一种复合纳米同轴电缆及其制备方法 |
RU2528985C2 (ru) * | 2012-07-03 | 2014-09-20 | Общество с ограниченной ответственностью "НаноТехЦентр" | Способ модифицирования углеродных нанотрубок |
JP5497109B2 (ja) | 2012-07-03 | 2014-05-21 | 昭和電工株式会社 | 複合炭素繊維 |
CN103594681B (zh) * | 2012-08-13 | 2016-06-08 | 清华大学 | 锂离子电池负极的制备方法 |
CN103594710A (zh) * | 2012-08-13 | 2014-02-19 | 清华大学 | 锂离子电池负极的制备方法 |
KR101451354B1 (ko) * | 2012-12-11 | 2014-10-15 | 인하대학교 산학협력단 | 독립형 탄소나노튜브/금속 산화물 입자 복합체 필름 및 그 제조방법 |
US9153814B2 (en) | 2012-12-19 | 2015-10-06 | Toyota Motor Engineering & Manufacturing North America, Inc. | Mesoporous starburst carbon incorporated with metal nanocrystals or metal oxide nanocrystals, and uses thereof |
CN103035897B (zh) * | 2012-12-20 | 2015-03-25 | 中国东方电气集团有限公司 | 一种锂电池锡基复合球形硬炭微球负极材料及其制备方法 |
CN103746099B (zh) * | 2014-01-17 | 2015-10-28 | 江苏华盛精化工股份有限公司 | 一种二氧化锡包裹的碳纤维材料的制备方法、产品及应用 |
US10003075B2 (en) | 2014-06-12 | 2018-06-19 | Council Of Scientific And Industrial Research | Carbon nanotube-metal nanocomposites as flexible, free standing, binder free high performance anode for Li-ion battery |
CN104176795B (zh) * | 2014-08-28 | 2016-01-20 | 扬州大学 | 负载大孔锑锡氧化物的二氧化钛纳米管的制备方法 |
CN104986753B (zh) * | 2015-06-25 | 2017-08-04 | 清华大学 | 超长碳纳米管及其制备方法和装置 |
CN105236387B (zh) * | 2015-11-13 | 2017-08-29 | 山东大学 | 一种碱性处理碳纳米管提高其水溶液分散性的方法 |
CN105529455B (zh) * | 2016-01-25 | 2018-07-17 | 陕西科技大学 | 一种棱柱组装球状SnO2钠离子电池负极材料及其制备方法 |
CN105702937B (zh) * | 2016-04-08 | 2018-10-26 | 扬州大学 | 一种SnO2/C纤维的制备方法 |
CN106058189B (zh) * | 2016-07-19 | 2019-04-05 | 天津师范大学 | 一种合成锂离子电池高容量负极材料的方法 |
RU2664525C1 (ru) * | 2017-05-23 | 2018-08-20 | Федеральное государственное бюджетное учреждение науки Омский научный центр Сибирского отделения Российской академии наук (ОНЦ СО РАН) | Способ получения нанокомпозита |
FR3099298B1 (fr) * | 2019-07-24 | 2021-06-25 | Centre Nat Rech Scient | Composite SnOx/C fluoré pour matériau d’électrode |
CN111453766A (zh) * | 2020-04-09 | 2020-07-28 | 吉林大学 | 一种一维MWCNTs@SnO2核壳结构及其制备方法以及在铅炭电池正极的应用 |
CN112794360B (zh) * | 2020-12-31 | 2023-04-14 | 鸡西市唯大新材料科技有限公司 | 一种制备纳米SnO2/GC复合负极材料的方法 |
CN113355687B (zh) * | 2021-04-20 | 2022-05-24 | 广东石油化工学院 | 一种锡基双金属碳化物@碳纳米链核壳结构及其制备方法和应用 |
CN114597369B (zh) * | 2022-03-16 | 2023-08-01 | 四川轻化工大学 | 一种碳锡纳米复合材料及其制备方法和应用 |
CN116885198B (zh) * | 2023-09-08 | 2023-12-08 | 浙江帕瓦新能源股份有限公司 | 前驱体及制备方法、正极材料、钠离子电池 |
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2008
- 2008-12-11 FR FR0858459A patent/FR2939786B1/fr not_active Expired - Fee Related
-
2009
- 2009-12-04 CN CN2009801561782A patent/CN102307807A/zh active Pending
- 2009-12-04 US US13/133,835 patent/US20110297889A1/en not_active Abandoned
- 2009-12-04 KR KR1020117013273A patent/KR20110094186A/ko not_active Application Discontinuation
- 2009-12-04 JP JP2011540157A patent/JP2012511492A/ja not_active Withdrawn
- 2009-12-04 EP EP09803810A patent/EP2356070A1/fr not_active Withdrawn
- 2009-12-04 WO PCT/FR2009/052408 patent/WO2010066989A1/fr active Application Filing
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US20110297889A1 (en) | 2011-12-08 |
WO2010066989A1 (fr) | 2010-06-17 |
CN102307807A (zh) | 2012-01-04 |
FR2939786A1 (fr) | 2010-06-18 |
JP2012511492A (ja) | 2012-05-24 |
FR2939786B1 (fr) | 2011-03-25 |
KR20110094186A (ko) | 2011-08-22 |
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