EP2409350A1 - Materiaux composites a base de liants fluores et nanotubes de carbone pour electrodes positives de batteries lithium - Google Patents

Materiaux composites a base de liants fluores et nanotubes de carbone pour electrodes positives de batteries lithium

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Publication number
EP2409350A1
EP2409350A1 EP10716553A EP10716553A EP2409350A1 EP 2409350 A1 EP2409350 A1 EP 2409350A1 EP 10716553 A EP10716553 A EP 10716553A EP 10716553 A EP10716553 A EP 10716553A EP 2409350 A1 EP2409350 A1 EP 2409350A1
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EP
European Patent Office
Prior art keywords
composite material
suspension
electrode
pvdf
weight
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.)
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Application number
EP10716553A
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German (de)
English (en)
French (fr)
Inventor
Dominique Plee
Bernard Lestriez
Sabrina Desaever
Dominique Guyomard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Arkema France SA
Original Assignee
Centre National de la Recherche Scientifique CNRS
Arkema France SA
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Application filed by Centre National de la Recherche Scientifique CNRS, Arkema France SA filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP2409350A1 publication Critical patent/EP2409350A1/fr
Withdrawn legal-status Critical Current

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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates generally to the field of storage of electrical energy in lithium secondary batteries Li-ion type. More specifically, the invention relates to a positive electrode material of Li-ion battery, its method of preparation and its use in Li-ion battery. The invention also relates to Li-ion batteries manufactured by incorporating this composite electrode material.
  • the electrode material according to the invention can be used in a non-aqueous electrolyte Li-ion secondary battery, to which it confers excellent capacitance and cycling characteristics under high current density.
  • a Li-ion battery includes at least one negative or anode electrode coupled to a copper current collector, a positive electrode or cathode coupled to an aluminum current collector, a separator, and an electrolyte.
  • the electrolyte consists of a lithium salt, generally lithium hexafluorophosphate, mixed with a solvent which is a mixture of organic carbonates, chosen to optimize the transport and dissociation of the ions.
  • a high dielectric constant favors the dissociation of the ions, and therefore the number of available ions in a given volume, whereas a low viscosity is favorable for the ionic diffusion which plays a key role, among other parameters, in the rates of charge and discharge of the electro-chemical system.
  • An electrode generally comprises at least one current collector on which is deposited a composite material which consists of: a so-called active material because it exhibits an electrochemical activity with respect to lithium, a polymer which acts as a binder and which is generally a copolymer of vinylidene fluoride for the positive electrode and water-based binders of the carboxymethylcellulose type or styrene-butadiene latexes for the negative electrode, plus an electronically conductive additive which is generally carbon black Super P or black acetylene.
  • a composite material which consists of: a so-called active material because it exhibits an electrochemical activity with respect to lithium, a polymer which acts as a binder and which is generally a copolymer of vinylidene fluoride for the positive electrode and water-based binders of the carboxymethylcellulose type or styrene-butadiene latexes for the negative electrode, plus an electronically conductive additive which is generally carbon black Super P or black acetylene.
  • Li-ion batteries Conventional active materials are graphite at the negative electrode and cobalt oxide at the positive electrode.
  • Li-ion batteries mainly resides today in the fields of mobile phones, computers and light tools, but there are some niche markets such as space, aeronautics and defense applications.
  • electrochemical storage seems to be a method of choice to allow optimal use and management of energy production by intermittent renewable energies such as photovoltaic and wind power.
  • Li-ion batteries have the highest energy density among rechargeable systems and are therefore widely considered as a source of electrical energy in electric vehicles and hybrid vehicles of the future. , especially those that would recharge directly on the sector.
  • Li-ion batteries have some disadvantages, particularly related to safety (possibility of decomposition of the electrolyte and solvent with release of gas, risk of explosion and / or ignition) and the cost of the stored kWh still high , which led to many works on alternative active materials, both at the positive electrode (phosphates, various oxides, ...), and the negative electrode (silicon, tin, various alloys, etc.). ).
  • Cobalt oxide has a significant voltage difference to lithium, good capacity and very good aging ability, but runaway reactions can occur and result in overheating, decomposition of solvent and electrolytes, even explosions and fires, if the internal pressure exceeds the resistance of the battery envelope. For the automotive application, this characteristic is unacceptable. In addition, cobalt is now part of the expensive materials and whose availability is limited. Tests conducted with LiNiO 2 , LiMnO 2 , LiMn 2 O 4 have drawbacks, either because the capacity is lower, or because the aging is bad, although generally, the safety aspect is improved.
  • JP 2008-300189 it has been proposed to use a vanadium-based system, in particular vanadium pentoxide V2O5 as the active material of a Li-ion battery positive electrode composite material, in association with a carbon-based electronic conduction agent such as carbon black, carbon nanotubes and a polymeric binder.
  • a vanadium-based system in particular vanadium pentoxide V2O5
  • a carbon-based electronic conduction agent such as carbon black, carbon nanotubes and a polymeric binder.
  • CN 101 192 682 discloses a Li-ion secondary battery comprising an anode consisting of a mixture of a lithium complex oxide, such as a mixed oxide Ni-Co-Li, Mn-Li or Mn-B-Li , with carbon nanotubes as conductive agents in a proportion ranging from 0.1 to 3% by weight and a polymeric binder such as PVDF or PTFE.
  • a lithium complex oxide such as a mixed oxide Ni-Co-Li, Mn-Li or Mn-B-Li
  • carbon nanotubes as conductive agents in a proportion ranging from 0.1 to 3% by weight
  • EP 2 034 541 discloses a method for preparing a lithium battery positive electrode composite material comprising lithium manganate, CNTs, carbon black and a fluoropolymer binder.
  • a method for preparing a battery electrode comprising preparing a resin / NTC masterbatch, which is added to a dispersion of electrode active material, the pasty mixture obtained being then applied to an electrode substrate.
  • the active material for secondary battery lithium electrode is preferably selected from transition metal oxides, such as lithium cobalt oxide LiCoO 2, LiNiO 2 the lithium nickel oxide, lithium manganese oxide LiMn 2 O 4 or mixed oxides based on several transition metals.
  • Li-ion optimally meeting the above criteria.
  • the production of high-performance electrodes based on polyanionic framework compounds with levels of NTC-type conductive additive as low as 1 to 2.5% has proved quite surprising.
  • the invention relates to a Li-ion battery positive electrode composite material, comprising: a) at least one conductive additive comprising carbon nanotubes at a rate ranging from 1 to 2.5% by weight; weight, preferably from 1.5 to 2.2% by weight relative to the total weight of the composite material; b) an electrode active material capable of reversibly forming an insertion compound with lithium, having an electrochemical potential greater than 2V with respect to the Li / Li + pair; c) a polymeric binder, characterized in that said insertion compound with lithium is chosen from polyanionic framework compounds of LiM y (XO z ) n type where: M represents a metal atom containing at least one of the metal atoms selected from the group consisting of Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, B and Mo, and where X represents one of the atoms selected from the group formed by P, Si, Ge, S and As.
  • M represents a metal atom
  • the polyanionic framework compounds are phosphates or mixed silicates of lithium and metal atom M, more particularly it is mixed phosphates.
  • the polyanionic framework compounds have a Masicon or Olivine type structure.
  • M is selected from Fe, Mn or combination thereof.
  • the lithium insertion compound is LiFePO 4 .
  • the CNTs used in the constitution of the composite material according to the invention have a fibril morphology. They generally have diameters of 10 to 50 nm, preferably 10 to 20 nm on average.
  • the length of the carbon nanotubes is generally of the order of 5-15 ⁇ m, but some dispersion methods can reduce it, in particular ultrasound.
  • This conductive additive differs from the usual conductive additives, such as SP carbon, acetylene black or graphite, by a very high form factor. This is defined by the largest dimension ratio on the smallest dimension of the particles. This ratio is of the order of 30 to 1000 for CNTs, against 3 to 10 for SP carbon, acetylene black and graphite.
  • the CNTs play an important role in the electrode composite material with respect to the maintenance of the capacitance as a function of the current density, the maintenance of the cycling capacity, which allows an excellent stability in cycling, and this at the same time.
  • high contents of active material for example up to 94%) in the electrode composite material.
  • the carbon nanotubes used in the constitution of the composite material according to the invention have a transition metal content of less than 1000 ppm by weight, measured by conventional chemical analysis and preferably less than 500 ppm. Too high levels of transition metals are expected to decrease the life of the batteries, especially at high temperatures and increase the risk of use. However, obtaining such nanotubes can be expensive and lead to excessive battery manufacturing costs.
  • conductive additives may be added in the composite material: graphite, carbon black such as acetylene black, SP carbon, carbon nanofibers.
  • Commercial conductive additives meet this requirement. These include in particular compounds Ensagri Super S ® or Super P® sold by Chemetals the VGCF nanofibers sold by Showa Denko.
  • the polymeric binder may be chosen from: polysaccharides, modified polysaccharides, latices, polyelectrolytes, polyethers, polyesters, polyacrylic polymers, polycarbonates, polyimines, polyamides, polyacrylamides, polyurethanes, polyepoxides, polyphosphazenes, polysulfones, halogenated polymers.
  • halogenated polymer there may be mentioned homopolymers and copolymers of vinyl chloride, vinylidene fluoride, vinylidene chloride, ethylene tetrafluoride, chlorotrifluoroethylene, and copolymers of vinylidene fluoride and of hexafluoropropylene (PVdF-HFP).
  • homopolymers and copolymers of acrylamide of acrylic acid, homopolymers and copolymers of maleic acid, homopolymers and copolymers of maleic anhydride, homopolymers and copolymers of acrylonitrile, homopolymers and copolymers of vinyl acetate and vinyl alcohol, homopolymers and copolymers of vinyl pyrrolidone, polyelectrolytes such as the homopolymers and copolymers of vinyl sulfonic acid, phenyl sulphonic acid, homopolymers and copolymers of allylamine, diallyldimethylammonium, vinylpyridine, aniline, ethylenimine.
  • aqueous dispersions of polymers known as latex based on vinyl acetate, acrylic, nitrile rubber, polychloroprene, polyurethane, acrylic styrene and styrene butadiene may be mentioned.
  • copolymer is meant in the present text, a polymer compound obtained from at least two different monomers.
  • Polymer blends are also interesting. There may be mentioned mixtures of carboxymethyl cellulose with latex styrene-butadiene, acrylic, and nitrile rubber.
  • Water soluble polymers are particularly preferred.
  • aqueous latexes of copolymers or fluorinated homopolymers are particularly preferred.
  • the polymeric binder is chosen from the group: PVDF, PVDF-HFP or PVDF-CTFE copolymers, PVDF and PVDF mixtures containing polar functional groups, and fluorinated terpolymers.
  • the invention relates to a method for preparing an electrode composite material, which comprises the following operations: i) preparation of a suspension or dispersion comprising in the end:
  • an additional conductive additive optionally an additional conductive additive; a polymeric binder;
  • the polymer is introduced in the pure state or in the form of a solution in a volatile solvent; the CNTs are introduced in the pure state or in the form of a suspension in a volatile solvent.
  • the CNTs are those marketed under the name of
  • the CNTs are multiwall nanotubes having from 5 to 15 walls, an average outer diameter of from 10 to 15 nm and a length ranging from 0.1 to 10 .mu.m.
  • Carbon nanotubes are difficult to disperse. Nevertheless, thanks to the method according to the invention, it is possible to distribute them in the electrode composite material in such a way that they form a mesh around the particles of active material and thus play a role of both a conductive additive but also mechanical maintenance, important to accommodate the volume variations during the charging-discharging steps. On the one hand, they distribute electrons to the particles of active material and, on the other hand, because of their length and flexibility, they form electric bridges between the particles of active material that move as a result of their volume variation.
  • the usual conductive additives SP carbon, acetylene black and graphite
  • the electrical paths are formed by the juxtaposition of grains and the contacts between them are easily broken following the volume expansion of the particles of the active material.
  • the volatile solvent is an organic solvent or water or a mixture of organic solvent and water.
  • Organic solvents include N-methyl pyrrolidone (NMP) or dimethyl sulfoxide (DMSO) or dimethylformamide (DMF).
  • the preparation of the suspension can be carried out in a single step or in two or three successive steps.
  • one embodiment consists of mixing all the components, followed by the mechanical dispersion step.
  • one embodiment consists in preparing a first dispersion containing the solvent, the CNTs and optionally all or part of the polymeric binder, by mechanical means, and then adding to this first dispersion. the other constituents of the composite material, this new suspension being used for the preparation of the final film.
  • one embodiment consists in preparing a dispersion containing the CNTs and optionally all or part of the polymeric binder in a solvent, then adding the active material, removing the solvent to obtain a powder, then forming a new suspension by adding solvent and the remaining components of the composite material to this powder, this new suspension being used for the preparation of the final film.
  • a preferred method for forming and homogenizing the dispersion is to prepare a slurry of solvent, polymer and CNTs which is subjected to the mechanical dispersion process prior to the addition of the active material.
  • Another preferred method for forming and homogenizing the dispersion is to prepare a suspension of solvent and CNT which is subjected to said mechanical dispersion process, before adding the binders and the active material.
  • the level of performance achieved for the Li-ion battery incorporating the positive electrode composite material obtained according to the method of the invention results from the conditions of preparation of said material, especially the step pre-dispersion of CNTs by grinding, and the quality of the dispersion, which is preferably carried out over a long period, generally greater than 10 hours, not obvious to those skilled in the art.
  • J.-H. Lee et al., J. Power Sources 184 (2008) 308 which observes a degradation of the CNTs during their dispersion by ultrasound.
  • the quality of the dispersion is evaluated on the basis of the values of the storage module G 'that are obtained by rheological measurements in frequency, which measures give access to two parameters G' and G ", respectively storage module and module. loss.
  • the suspension of NTC prepared according to the invention has, for a frequency of 1 Hz, a storage module
  • G 'as follows: ranging from 200 to 1000 Pascal, on a suspension of nanotubes in NMP at 2.2% by weight, and greater than or equal to 100 Pascal on a suspension of nanotubes (at 2.2% by weight) and PVDF (4.4% by weight) in NMP.
  • the film can be obtained from the suspension by any conventional means, for example extrusion, spreading (tap casting) or spraying (spray drying) on a substrate followed by drying.
  • a metal sheet capable of serving as a collector for the electrode, for example an aluminum foil or grid treated with an anti-corrosion coating.
  • the substrate film thus obtained can be used directly as an electrode.
  • This film can optionally be densified by applying a pressure (between 0.1 and 10 tonnes / cm 2 ).
  • the composite material according to the invention is useful for the elaboration of electrodes for electrochemical devices, in particular in lithium batteries.
  • Another object of the invention is constituted by a positive battery electrode
  • Li-ion comprising at least one current collector on which is deposited a composite material according to the invention or obtained according to the process of the invention.
  • a lithium battery comprises a negative electrode constituted by lithium metal, a lithium alloy or a lithium insertion compound and a positive electrode, the two electrodes being separated by a solution of a salt whose cation contains at least one lithium ion, for example LiPF 6 , LiAsF 6 , LiClO 4 , LiBF 4 , LiC 4 BO 8 , Li (C 2 F 5 SO 2 N, O [(C 2 Fs) 3 PF 3 ], LiCF 3 SO 3 , LiCH 3 SO 3 , and LiN (SO 2 CF 3 ) 2 , LiN (SO 2 F) 2 , ... in an aprotic solvent (ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl carbonate ...), all serving as electrolyte.
  • a salt whose cation contains at least one lithium ion, for example LiPF 6 , LiAsF 6 , LiClO 4 , LiBF 4 , LiC 4 BO 8 , Li
  • the positive electrode consists of the composite material whose active ingredient represents from 80% to 97%.
  • the content of polymeric binder is between 0.1 and 10% and the content of carbon nanotubes is between 1% and 2.5%, preferably between 1.5% and 2.2% by weight of the weight of the carbon nanotubes. dry electrode.
  • the invention also relates to the use of a composite material comprising: a) at least one conductive additive comprising carbon nanotubes at a level ranging from 1 to 2.5% by weight, preferably from 1.5 to 2, 2% by weight relative to the total weight of the composite material; b) an electrode active material capable of reversibly forming an insertion compound with lithium, having an electrochemical potential greater than 2V with respect to the Li / Li + pair, said lithium insertion compound being selected from polyanionic framework compounds of the LiM y (XO z ) n type where: M represents a metal atom containing at least one of the metal atoms selected from the group formed by Mn, Fe, Co, Ni, Cu, Mg, Zn, V , Ca, Sr, Ba, Ti, Al, Si, B and Mo, and where X represents one of the atoms selected from the group formed by P, Si,
  • a binder consisting of a polymer or a mixture of polymeric binders
  • the invention also relates to the use of a composite material obtained according to the process described above, for the manufacture of Li-ion batteries.
  • Example 1 The present invention is illustrated by the following examples, to which it is however not limited.
  • Example 1 The present invention is illustrated by the following examples, to which it is however not limited.
  • the composite material consists of 94% by weight of CZLiFePO 4 with a carbon coating, the latter representing 1-3% of the total mass of CZLiFePO 4 , 4% by weight of the PVDF binder supplied by Arkema under the brand name Kynar ® of which 1/3 consists of Kynar ® ADX and 2/3 of Kynar ® HSV 900, and 2% by mass of NTC supplied by Arkema under the name Graphistrength ® ClOO.
  • These nanotubes have an average diameter of 20 nm, a length estimated at a few microns and their chemical composition shows that they contain about 7% of mineral ash from the synthesis process.
  • the mixture is co-milled in a chromium-plated stainless steel jar with a volume of 250 ml containing a mixture of chrome-plated stainless steel balls of diameter 10 and 5 mm by a planetary mill for 24 hours. After drying at 120 ° C., the mixture is treated at 600 ° C. for 6 h in an Argon atmosphere (with 2% H 2 ).
  • the NTC is first dispersed using a ball mill (Pulverisette 7 Fritsch) all the CNTs used in the composition of the composite material.
  • the conditions of the dispersion are 700 rpm, a 12.5 ml crushing bowl containing 3 beads of 10 mm diameter, 0.360 ml of NMP, 8 mg of NTC.
  • the duration of the dispersion varies from 6 to 48 hours.
  • the CNT particles are added to the dispersion.
  • the electrode is prepared by coating the suspension containing the composite on a 25 ⁇ m thick aluminum current collector. The height of the squeegee of the coating machine is set at 180 ⁇ m. The electrode is dried overnight in an oven at 70 ° C. Then it is densified under 62.5 MPa. It is then dried again overnight in an oven at 70 0 C, and finally Ih at 100 0 C under vacuum. After drying, the amount of electrode deposited per unit area of current collector is measured: 4 mg / cm 2 .
  • the electrode thus obtained was mounted in a battery having as negative electrode a lithium metal sheet laminated on a nickel current collector, a fiberglass separator, a liquid electrolyte consisting of a solution
  • Electrochemical performance evaluation was performed in the 2-4.3 V potential range. Li + / Li, in galvanostatic mode. A current I of 1 A / g corresponds to a regime of 6C (charging time or discharge 10 minutes).
  • FIG. 1 represents the evolution of the capacity Q (in mAh / g) at a rate of 6C (1 A / g) as a function of the duration of the dispersion of the CNTs. The best electrochemical performances are obtained for an optimal dispersion time of 15h.
  • the attached Figure 2 gives the rheological characteristics of the dispersion of
  • composition of the composite material of this example is identical to that of Example 1.
  • the preparation differs from that given in Example 1 in that the PVDF binder is introduced, in powder form, during the first stage. , ie during the dispersion of the CNTs.
  • the NTCs and PVDFs used in the composition of the composite material are first dispersed in NMP using a ball mill (Pulverisette 7 Fritsch).
  • the conditions of dispersion are 700 rpm, a 12.5 ml milling bowl containing 3 beads of 10 mm diameter, 0.360 ml of NMP, 8 mg of NTC, 16 mg of PVDF.
  • the duration of the dispersion varies from 6 to 48 hours.
  • the particles of CZLiFePO 4 (376 mg) and 0.640 ml of NMP are added, and the whole is mixed by co-grinding at 700 rpm for 1 h 30 min.
  • the composite material constitutes 29% by weight of the suspension, the rest is NMP.
  • the electrode and the battery are then prepared, and the electrochemical performances evaluated as in Example 1.
  • Figure 3 shows the evolution of the capacity Q (in mAh / g) at a rate of 6C as a function of the duration of the dispersion of the mixture NTC + PVDF. The best electrochemical performances are obtained for an optimal dispersion time of 24 hours.
  • Example 3 The composition of the composite material of this example is identical to that of Example 1.
  • the preparation differs from that given in Example 1 by the following characteristics: in the first step, the duration of the dispersion of the CNTs is 3 pm in the second step, the composite material constitutes 32% by weight of the suspension; and in the third step, the height of the doctor blade is fixed at 300 ⁇ m and the densification pressure is 750 MPa. After the third step, the amount of electrode deposited per unit area of the current collector is measured: 7 mg / cm 2 .
  • the electrode (a) thus obtained was mounted in a battery having as negative electrode a lithium metal sheet laminated on a nickel current collector, a fiberglass separator, a liquid electrolyte consisting of a 1M LiPF solution. 6 dissolved in EC / DMC 1: 1.
  • the comparison of the curves shows a better maintenance of the capacitance as a function of the current density for the electrode according to the invention.
  • the capacity restored at a rate of 6C is 120 mAh / g of CZLiFePO 4 with CNTs, 100 mAh / g with acetylene black, and 85 mAh / g with VGCF.
  • the restored capacity is brought back to the electrode mass, the following results are obtained: 113 mAh / g of electrode with the CNTs, 91 mAh / g with the acetylene black, and 78 mAh / g with the VGCF, which demonstrate the superiority of the electrode (a) according to the invention.
  • composition of the composite material of this example is 94.3% CZLiFePO 4 , 1.7% NTC, 4% PVDF. It was prepared in the same way as the material of Example 3.
  • the electrode (a) thus obtained was mounted in a battery having as negative electrode a lithium metal sheet laminated on a nickel current collector, a fiberglass separator, a liquid electrolyte consisting of a 1M LiPF solution. 6 dissolved in EC / DMC 1: 1.
  • Figure 5 shows the evolution of the capacity Q (in mAh / g) as a function of the number of cycles for the three samples (a), (b) and (c).
  • the mass current under load corresponds to a regime of C and discharged at a rate of 2C.
  • composition of the composite material of this example is 94.3% CZLiFePO 4 , 1.7% NTC, 4% PVDF. It was prepared in the same way as the material of Example 4, with one difference, namely that the CNTs were purified so as to decrease the iron content. After treatment, it was 215 ppm.
  • the electrode (a ') thus obtained was mounted in a battery having as negative electrode a lithium metal sheet laminated on a nickel current collector, a fiberglass separator, a liquid electrolyte consisting of a 1M solution. LiPF 6 dissolved in EC / DMC 1: 1. The electrochemical performances were measured and compared to those of similar batteries in which the positive electrode is an electrode whose initial composition is:
  • Table 1 shows the performance comparison for the four systems, in initial and final capacities.
  • Table 1 The comparison of the figures shows a better maintenance of the capacity according to the cycling for the electrode incorporating purified nanotubes according to the invention than for all the other additives tested.
  • composition of the composite material of this example is similar to that of Examples 1 to 3, 94% C / LiFePO 4 , 2% NTC, 4% PVDF. It is prepared as follows: first of all, in the NMP, all the CNTs entering the composition of the composite material are dispersed. At the end of the dispersion, the particles of CZLiFePO 4 and NMP are added, and the whole is mixed by co-grinding. The NMP is then removed by drying and the resulting powder is recovered. It is then dispersed in a solution of PVDF in NMP.
  • the NTC is first dispersed using a ball mill (Pulverisette 7 Fritsch) all the CNTs used in the composition of the composite material.
  • the conditions of dispersion are 700 rpm during
  • the particles of C / LiFePO 4 (447.4 mg) and 0.640 ml of NMP are added to the CNT dispersion, and the whole is mixed by co-grinding at 700 revolutions per minute for 1 h 30 min.
  • the suspension is dried overnight in an oven at 70 ° C. at the end of which a powder consisting of 2.1% by weight of CNT and 97.9% by weight of C / LiFePO 4 is recovered.
  • this powder and 19 mg of PVDF is dispersed in 1 ml of NMP by co-milling at 700 rpm for 1 h 30 min.
  • the composite material constitutes 32% by weight of the suspension, the rest is NMP.
  • the electrode is prepared by coating the suspension containing the composite on a 25 ⁇ m thick aluminum current collector.
  • the height of the squeegee of the coating machine is fixed at 300 ⁇ m.
  • the electrode is dried overnight in an oven at 70 ° C. Then it is densified under 750 MPa. It is then dried again overnight in an oven at 70 0 C, and finally Ih at 100 0 C under vacuum. After drying, the amount of electrode deposited per unit area of current collector is measured: 9 mg / cm 2 .
  • the electrode thus obtained was mounted in a battery having as negative electrode a lithium metal foil laminated on a nickel current collector, a fiberglass separator, a liquid electrolyte consisting of a 1M LiPF 6 solution dissolved in EC / DMC 1: 1.
  • Figure 6 shows the evolution of the capacity Q (in mAh / g) as a function of the number of cycles at a rate of C / 5 and in discharge at a rate of D / 2.5.
  • Figure 7 shows the evolution of the capacitance Q (in mAh / g) as a function of the mass current. It is observed that the composite material according to the invention has good electrochemical performance.
  • composition of the composite material of this example is 94% CZLiFePO 4 , 2% NTC, 4% of a mixture of carboxymethyl cellulose (CMC) and styrene butadiene (SBR).
  • the NTC is first dispersed using a ball mill (Pulverisette 7 Fritsch) all the CNTs used in the composition of the composite material.
  • the conditions of the dispersion are 700 rpm for 15 hours, a 12.5 ml crushing bowl containing 3 beads of 10 mm diameter, 0.360 ml of NMP, 9.6 mg of NTC.
  • a second step the particles of C / LiFePO 4 (447.4 mg) and 0.640 ml of NMP are added to the dispersion of the CNTs and the whole is mixed by co-grinding at 700 revolutions per minute for 1 h 30 min.
  • the suspension is dried overnight in an oven at 70 ° C. at the end of which a powder consisting of 2.1% by weight of CNT and 97.9% by weight of C / LiFePO 4 is recovered.
  • this powder and 19 mg of CMC + SBR is dispersed in 1 ml of deionized water by co-grinding at 700 rpm for 1 h 30 min.
  • the composite material constitutes 32% by weight of the suspension, the remainder is deionized water.
  • the electrode is prepared by coating the suspension containing the composite on a 25 ⁇ m thick aluminum current collector.
  • the height of the squeegee of the coating machine is fixed at 300 ⁇ m.
  • the electrode is dried overnight at room temperature. Then it is densified under 750 MPa. It is then dried Ih at 100 ° C. under vacuum. After drying, the amount of electrode deposited per unit area of the current collector is measured: 6 mg / cm 2 .
  • the electrode thus obtained was mounted in a battery having as negative electrode a lithium metal foil laminated on a nickel current collector, a fiberglass separator, a liquid electrolyte consisting of a 1M LiPF 6 solution dissolved in EC / DMC 1: 1.
  • Electrochemical performance evaluation was performed in the 2-4.3 V potential range. Li + / Li.
  • Figure 6 shows the evolution of the capacity Q (in mAh / g) as a function of the number of cycles at a rate of C / 5 and in discharge at a rate of D / 2.5.
  • Figure 7 shows the evolution of the capacitance Q (in mAh / g) as a function of the mass current. It is observed that the composite material according to the invention has good electrochemical performance.
  • buttons cell comprising: the positive 40% of crude nanotubes whose iron content is of the order of 3%, and 60% of PVDF coated on aluminum at various thicknesses; to the negative, lithium metal; - as electrolyte, EC-DMC (1/1) with HPF6 (IM) These cells are then cycled in cyclic voltammetry on a VMP 2 bench between 2 and 4.3
  • the iron is in stable form, that it does not dissolve in the electrolyte and remains contained in the positive electrode. It undergoes, however, perfectly reversible oxidation-reduction phenomena.

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  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
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  • Battery Electrode And Active Subsutance (AREA)
EP10716553A 2009-03-19 2010-03-18 Materiaux composites a base de liants fluores et nanotubes de carbone pour electrodes positives de batteries lithium Withdrawn EP2409350A1 (fr)

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FR0901279A FR2943463B1 (fr) 2009-03-19 2009-03-19 Materiaux composites a base de liants fluores et nanotubes de carbone pour electrodes positives de batteries lithium.
PCT/FR2010/050485 WO2010106292A1 (fr) 2009-03-19 2010-03-18 Materiaux composites a base de liants fluores et nanotubes de carbone pour electrodes positives de batteries lithium

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US20120028117A1 (en) 2012-02-02
FR2943463A1 (fr) 2010-09-24
JP5684226B2 (ja) 2015-03-11
KR20110136867A (ko) 2011-12-21
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