• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to the field of lead batteries. More particularly, the present invention relates to a solid composition comprising from 5 to 60% by weight of carbon nanofillers, preferably carbon nanotubes, dispersed in a water-soluble polymer in the presence of at least one cationic component chosen from alkali metal cations. or alkaline-earth and ammonium ions, and the use of this composition for the preparation of formulations for lead-acid battery electrode.
    公开号:FR3033327A1
    申请号:FR1551843
    申请日:2015-03-05
    公开日:2016-09-09
    发明作者:Alexander Korzhenko；Christophe Vincendeau；Patrick Delprat
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to the field of lead-acid batteries. More particularly, the present invention relates to a solid composition comprising carbon nanofillers dispersed in a water-soluble polymer in the presence of at least one cationic component selected from alkali or alkaline earth metal cations and ammonium ions, and the use of this solid composition for the preparation of formulations for lead battery electrode. STATE OF THE ART Today, lead-acid batteries are the most developed rechargeable electrochemical systems because of their high reliability and low cost compared to more recent systems under development such as lithium-ion batteries. Lead-acid batteries are mainly used to power the electric start of internal combustion engines, particularly vehicles, because they are able to provide a high intensity current, but they can also be used to store energy intermittently, such as solar or wind energy. A lead-acid battery is a series of elements (or cells) lead-acid connected in series and joined in the same box. The battery only provides electrical power if it has been previously charged. The elements are capable of storing and returning electrical energy by reversible electrochemical reactions occurring during charging / discharging cycles of the battery. The performance of a lead-acid battery is evaluated essentially by the maximum current that it can provide in a few moments, by its capacity of storage of the available energy, and by the number of cycles of charge / discharge before complete discharge resulting by a lifetime of the battery.
    [0002] Typically, in a lead-acid battery, each cell comprises an assembly of electrodes (anode and a cathode), which are connected to a sulfuric acid type electrolyte, and the cells are separated from each other by a membrane which can be polypropylene for example. The anode consists mainly of lead oxide, and the lead sponge cathode finely distributed, and they are made with a current collector 5 generally made of lead or a lead alloy such as Pb / Sb or Pb / Ca. Sulfuric acid, in the form of dilute aqueous solution or gel, feeds a flow of sulfate ions between the electrodes. The discharge / charge cycles of the battery thus result in a process of sulfation of the electrodes during the discharge, which is reversible during charging. But under certain conditions, the sulfation can generate a stable deposit of lead sulphate on the electrodes, which prevents the electrochemical reactions, in particular the oxidation of the lead during the charging, and thus the optimal use of the active material of the electrodes . The efficiency of the transfer of sulfated charges between the electrodes and the electrolyte is mainly responsible for the performance and longevity of the battery.
    [0003] Different ways have already been explored in the prior art to improve the performance of lead batteries, in particular the addition of carbon nanofillers such as carbon nanotubes, in the active material formulations of the electrodes. Carbon nanotubes (CNTs), consisting of coiled graphite sheets, are known for their excellent electrical conductivity, and are stable in acidic or corrosive environments. However, CNTs are difficult to handle and disperse, due to their small size, their powderiness and, possibly, when they are obtained by chemical vapor deposition (CVD), their entangled structure generating otherwise strong Van der Waals interactions between their molecules. The low dispersion of the CNTs in the matrices in which they are incorporated, in particular the aqueous electrode formulations, limits their effectiveness and may even affect the charge transfers between the electrode and the electrolyte and therefore the performance of the battery. In order to overcome the drawbacks associated with the incorporation of CNTs into lead-acid battery electrode formulations, it has been proposed to use NTCs functionalized with oxygen groups or with conductive polymers such as polythiophene, to improve their compatibility with the electrode formulation. This method, described in document WO 2013/011516, however generates an additional cost related to the nature of the added nanofillers. WO 2014/114969 proposes a dry route for the incorporation of carbon nanofillers, in particular crude CNTs, into a paste-like electrode formulation, consisting of preparing an intimate mixture of CNT and lead oxide in the form of powder, using different grinding technologies, for example with a ball mill. This mixture, comprising from 5 to 20% by weight of CNT in lead oxide can be used directly for the preparation of an electrode formulation, or it can be mixed with lead oxide to dope the latter. 10 carbon nanofillers. This approach is, however, difficult to industrialize, given the large quantities of powder co-grinding. It has also been suggested in WO 2014/141279 to spray a suspension of NTC in the form of droplets of predetermined size onto a matrix comprising lead oxide, in order to homogeneously incorporate CNTs into a electrode formulation. The suspension, with a concentration ranging from 0.005 to about 0.1% by weight, is prepared by adding the CNTs in an aqueous medium with mechanical stirring or under ultrasound. However, it is difficult to accurately determine the crude CNTs which are in the pulverulent state, at this level of low concentration.
    [0004] There is thus still a need for a simple, reliable and economical way to incorporate carbon nanotubes homogeneously into lead battery electrode formulations. Now the Applicant has discovered that this need could be satisfied by providing a solid composition comprising carbon nanotubes dispersed in a water-soluble polymer. WO 2011/0117530 discloses a masterbatch in solid form based on CNT, a polymeric binder may be a modified cellulose and optionally a solvent, used for the preparation of liquid formulations containing CNT, but its use for preparing lead-acid electrode formulations has not been contemplated.
    [0005] It has also appeared to the Applicant that the combination of a water-soluble polymer with a cationic component makes it possible to render the CNTs which are intrinsically hydrophobic, more easily compatible with aqueous systems. The invention thus provides a solid composition comprising carbon nanotubes dispersed in a water-soluble polymer in the presence of at least one cationic component selected from alkali or alkaline earth metal cations and ammonium ions. This composition is thus ready for use for easy and safe use in preparing formulations for the manufacture of electrodes in order to increase their electrical conductivity and improve the overall performance of lead-acid batteries. In addition, this invention can also be applied to other carbon nanofillers than carbon nanotubes, and in particular to graphene, or a mixture of carbon nanotubes and graphene in all proportions.
    [0006] SUMMARY OF THE INVENTION The present invention relates to a solid composition comprising from 5 to 60% by weight of carbon nanofillers dispersed in at least one water-soluble polymer in the presence of at least one cationic component selected from alkali metal cations. or alkaline earth and ammonium ions.
    [0007] The present invention provides a concentrated composition of carbon nanofillers, which makes it possible to obtain stabilized dispersions during the preparation of electrode formulations, and to create a better association of the carbon nanofillers particles with the various active constituents of the formulation, especially with lead or lead oxide. The composition according to the invention also contributes to limiting the phenomena of corrosion and cracking of the electrodes which limit the life of the battery. Thus, the invention also relates to the use of said composition for the preparation of a lead battery electrode formulation. Another aspect of the invention relates to a lead battery electrode 30 obtainable from said composition, as well as the lead battery comprising at least said electrode.
    [0008] DETAILED DESCRIPTION OF THE INVENTION The invention is now described in more detail and in a nonlimiting manner in the description which follows.
    [0009] Carbon nanofillers In the remainder of this description, "carbon nanofillers" are carbon nanotubes (CNTs), graphene, or a mixture of CNTs and graphene in all proportions. Preferably, the carbon nanofillers are carbon nanotubes.
    [0010] NTCs have particular, tubular, hollow crystalline structures derived from carbon. CNTs generally consist of one or more graphite sheets arranged concentrically about a longitudinal axis. One-sided nanotubes (Single Wall Nanotubes or SWNTs) and multiwall nanotubes (Multi Wall Nanotubes or MWNTs) are thus distinguished.
    [0011] The carbon nanotubes usually have a mean diameter ranging from 0.1 to 200 nm, preferably from 0.1 to 100 nm, more preferably from 0.4 to 50 nm and more preferably from 1 to 30 nm, or even from 10 to 15 nm, and advantageously a length of more than 0.1 μm and preferably 0.1 to 20 μm, preferably 0.1 to 10 μm, for example about 6 μm. Their length / diameter ratio is advantageously greater than 10 and most often greater than 100. Their specific surface area is, for example, between 100 and 300 m 2 / g, advantageously between 200 and 300 m 2 / g, and their apparent density may especially be between 0.01 and 0.5 g / cm3 and more preferably between 0.07 and 0.2 g / cm3. The multi-walled carbon nanotubes may for example comprise from 5 to 15 sheets and more preferably from 7 to 10 sheets.
    [0012] The CNTs can be produced by different processes, however the CNTs used in the composition according to the invention are synthesized by chemical vapor deposition (CVD) because this process is the most suitable for industrial manufacture in terms of CNT quality. An example of such crude carbon nanotubes is in particular the commercial name Graphistrength® C100 from Arkema. These nanotubes can be purified and / or treated (for example oxidized) and / or ground.
    [0013] The grinding of the nanotubes may in particular be carried out cold or hot and be carried out according to the known techniques used in devices such as ball mills, hammers, grinders, knives, jet gasses or any other grinding system capable of reducing the size of the entangled network of nanotubes. It is preferred that this grinding step is performed according to a gas jet milling technique and in particular in an air jet mill. The purification of the crude or milled nanotubes can be carried out by washing with a sulfuric acid solution, so as to rid them of any residual mineral and metal impurities, such as for example iron coming from their process of preparation. The weight ratio of the nanotubes to the sulfuric acid may especially be between 1: 2 and 1: 3. The purification operation may also be carried out at a temperature ranging from 90 to 120 ° C, for example for a period of 5 to 10 hours. This operation may advantageously be followed by rinsing steps with water and drying the purified nanotubes. The nanotubes may alternatively be purified by high temperature heat treatment, typically above 1000 ° C. The oxidation of the nanotubes is advantageously carried out by putting them in contact with a solution of sodium hypochlorite containing from 0.5 to 15% by weight of NaOCl and preferably from 1 to 10% by weight of NaOCl, for example in a weight ratio of nanotubes to sodium hypochlorite ranging from 1: 0.1 to 1: 1. The oxidation is advantageously carried out at a temperature below 60 ° C and preferably at room temperature for a time ranging from a few minutes to 24 hours. This oxidation operation may advantageously be followed by filtration and / or centrifugation, washing and drying steps of the oxidized nanotubes. Crude carbon nanotubes, optionally milled, that is to say nanotubes which are neither oxidized nor purified nor functionalized and have undergone no other chemical and / or thermal treatment, are preferably used in the present invention. Furthermore, it is preferred to use carbon nanotubes obtained from renewable raw material, in particular of vegetable origin, as described in application FR 2 914 634.
    [0014] The graphene which can be used in the composition according to the invention is obtained by chemical vapor deposition or CVD, preferably by a process using a powdery catalyst based on a mixed oxide. It is typically in the form of particles having a thickness of less than 50 nm, preferably less than 15 nm, more preferably less than 5 nm and less than one micron side dimensions, preferably less than 50 nm. 10 nm to less than 1000 nm, more preferably 50 to 600 nm, or even 100 to 400 nm. Each of these particles generally contains from 1 to 50 sheets, preferably from 1 to 20 sheets and more preferably from 1 to 10 sheets, or even from 1 to 5 sheets which can be disconnected from each other in the form of independent leaflets, for example during an ultrasound treatment. The Water-Soluble Polymer The water-soluble polymer may be ionic or nonionic. As water-soluble polymers, polysaccharides can be used in the present invention without this list being limiting; modified polysaccharides such as modified celluloses; polyethers such as alkylene polyoxides or polyalkylene glycols; lignosulfonates; polyacrylates; products based on polycarboxylic acids, especially polyether polycarboxylates or copolymers thereof; naphthalene sulfonates and their derivatives; and their corresponding aqueous solutions. Preferably, the water-soluble polymer is chosen from modified celluloses, in particular carboxymethylcellulose (CMC), lignosulphonates, polyether polycarboxylates or their copolymers, naphthalene sulphonates and their derivatives, and their corresponding aqueous solutions. For example, commercial products from the ETHACRYL® range or the Coatex XP 1824 can be used. Water-soluble polymers are generally commercially available in solid form, or as an aqueous solution of higher or lower viscosity. The cationic components The presence of a cationic component, in particular at least one cation of an alkaline or alkaline-earth metal or of ammonium ion, in the composition according to the invention contributes to ensuring the stabilization of the dispersion of the carbon nanocharges. It also makes it possible to limit corrosion problems in the electrode formulation.
    [0015] As the cationic component, the alkali metal or alkaline earth metal cations are preferred. As cations, there may be mentioned for example Na +, Li +, K +, Mg2 +, Ca2 +, Ba2 +, used alone or as a mixture, preferably the cations are Na +.
    [0016] The cationic components are present in the composition according to the invention, generally by introducing a base in aqueous solution, or they can be provided by the water-soluble polymer when it is in a salified form. The solid composition The solid composition according to the invention comprises from 5% to 60% by weight of carbon nanofillers relative to the total weight of the composition. According to one embodiment of the invention, the solid composition comprises from 18% to 50% by weight, preferably from 40% to 50% by weight of carbon nanofillers relative to the total weight of the composition. According to one embodiment of the invention, the solid composition comprises from 0.05% to 50% by weight of cationic component, and preferably from 0.05% to 10% by weight, more preferably from 0, From 5% to 5% by weight, or even from 0.1% to 3% by weight of cationic component, relative to the total weight of the composition. According to one embodiment of the invention, the water-soluble polymer represents from 20% to 80% by weight, preferably from 20% to 60% by weight, relative to the total weight of the composition. The composition according to the invention is in solid form, generally in agglomerated physical form such as granules. The composition according to the invention may further comprise water up to about 90% by weight and remain in a solid form. It is then in the form of a moist solid, generally comprising from 10% to 30% by weight, preferably from 18% to 25% by weight of CNT. The wet composition can then be dried to yield a concentrated composition preferably comprising from 40% to 50% by weight of CNT in agglomerated physical form. The composition according to the invention is advantageously prepared using a compounding device.
    [0017] By "compounding device" is meant an apparatus conventionally used in the plastics industry for the melt blending of thermoplastic polymers and additives in order to produce composites. In this apparatus, the water-soluble polymer and the carbon nanofillers in the presence of cations are mixed using a high-shear device, for example a co-rotating twin-screw extruder or a co-kneader. Examples of co-kneaders that can be used are the BUSS® MDK 46 co-kneaders and those of the BUSS® MKS or MX series, marketed by the company BUSS AG, all of which consist of a screw shaft provided with fins, arranged in a heating sleeve optionally consisting of several parts and whose inner wall is provided with kneading teeth adapted to cooperate with the fins to produce a shear of the kneaded material. The shaft is rotated and provided with oscillation movement in the axial direction by a motor. These co-kneaders may be equipped with a granule manufacturing system, adapted for example to their outlet orifice, which may consist of an extrusion screw or a pump. The co-kneaders that can be used preferably have an L / D screw ratio ranging from 7 to 22, for example from 10 to 20, while the co-rotating extruders advantageously have an L / D ratio ranging from 15 to 56, for example From 20 to 50. According to one embodiment, the solid state nanofillers and the solid water soluble polymer are simultaneously introduced into the same feed zone of the device, and an aqueous solution of a base is introduced into a zone of distinct power supply. According to one embodiment, the nanocharges in the solid state are introduced into a first feed zone of the device, and the water-soluble polymer in aqueous solution, salified or additive of a base, is introduced into a feed zone. separate. The mixing of the various constituents can be carried out at a temperature preferably between 20 ° C and 90 ° C. The dispersion of the nanofillers thus produced in the presence of the cations is effective and homogeneous during the compounding. The cations then promote the integration of these nanofillers in aqueous acidic formulations such as lead battery electrode formulations. By way of comparison, it has not been possible to obtain a composition comprising 20% of carbon nanotubes in an ethylene polyoxide in the absence of Nat cations. solid physical form agglomerated, for example in the form of granules, or in the form of rods which, after cooling, are cut into granules. The composition thus obtained may then optionally be dried, by any known method (ventilated oven or under vacuum, infra red, induction, microwave, etc ...), in particular to eliminate all or part of the water present and thus obtain a more concentrated composition in carbon nanofillers.
    [0018] The composition according to the invention may optionally be subjected to a grinding step according to the techniques well known to those skilled in the art, so as to obtain a composition in powder form. Use of the composition Another aspect of the invention relates to the use of a solid composition comprising from 5 to 60% by weight of carbonaceous nanofillers dispersed in at least one water-soluble polymer in the presence of at least one cationic component selected from alkali or alkaline earth metal cations and ammonium ions for preparing a lead battery electrode formulation.
    [0019] In this aspect, the composition according to the invention is used to homogeneously incorporate carbon nanofillers into a pasty composition for coating a solid current collector to form an electrode. The incorporation of the carbon nanofillers is facilitated because of their association with a water-soluble polymer thus giving them a hydrophilic character compatible with the aqueous formulations of the electrodes. The electrode may be an anode or a cathode. The electrode formulation, generally in the form of a pasty composition, may comprise lead oxide, water, sulfuric acid, mechanical reinforcing fillers such as glass fibers, carbon fibers or polyester fibers, and various compounds including barium sulfate or carbon black, or other electroactive compounds.
    [0020] By lead oxide is meant a mixture of lead oxides of formula PbOx with 1 <x <2, with the possible presence of unoxidized lead. Mixing of the constituents of the formulation to form the dough can be achieved in any type of mixing device, such as a blender, planetary mixer, screw mixer, etc. The proportions of the various compounds used in the electrode formulation are adjusted in such a way that the amount of carbon nanofillers varies advantageously from 0.0005% to 1% by weight relative to the weight of the formulation, preferably from 0.001% to 0%. , 5% by weight, preferably from 0.001% to 0.01% by weight relative to the weight of the formulation. The sulfuric acid may be present in a concentration ranging from 1 to 20 mol / l and preferably between 3 and 5 mol / l. The sulfuric acid may represent from 1% to 10%, preferably from 2 to 7% of the total weight of the formulation. The amount of water present in the pasty composition is between 7% and 20% by weight relative to the weight of the pasty composition. The mechanical reinforcing fillers, preferably glass fibers, are present at a content ranging from 0.1% to 1% by weight relative to the weight of the pasty composition. The invention also relates to a lead-acid battery electrode obtainable from a solid composition comprising from 5 to 60% by weight of carbon nanofillers dispersed in at least one water-soluble polymer in the presence of at least at least one cationic component selected from alkali or alkaline earth metal cations and ammonium ions. A method for preparing a lead battery electrode may comprise, for example, at least the following steps: a) providing a solid composition as described above; b) preparing a pasty composition comprising using the solid composition of step a); C) impregnating a grid with the pasty composition of step b); d) pressing followed by drying and maturation of the impregnated grid.
    [0021] It will be understood that the above method may comprise other preliminary, intermediate or subsequent steps, provided that they do not adversely affect the obtaining of the desired electrode. The grid can be flexible or rigid, or come in different forms. The grid is composed of lead or a lead-based alloy. After applying the paste to the grid, the drying is generally carried out at a temperature ranging from 30 ° C to 65 ° C, at least 80% relative humidity, for more than 18 hours. The maturation is then preferably carried out, for example from 55 ° C. to 80 ° C. under ambient relative humidity, for one to three days.
    [0022] The electrode according to the invention may be an anode or a cathode. The invention also relates to a lead battery comprising at least one electrode according to the invention. A lead-acid battery typically includes a separator between each pair of positive and negative electrodes. This separator may be any porous non-conductive material, for example a polypropylene or polyethylene sheet. Its thickness can vary from 0.01 to 0.1 mm. A pair of electrodes and a separator define a cell. The lead acid battery of the present invention may comprise from 1 to 12 cells, which can provide a voltage of 1.5 to 2.5 volts each. Incorporating the carbonaceous nanofillers using the composition of the invention significantly improves the number of charge / discharge cycles of the battery, and limits electrode cracking problems, and it extends the operational life of the battery. The invention will now be illustrated by the following examples, which are not intended to limit the scope of the invention as defined by the appended claims. EXPERIMENTAL PART Example 1: Preparation of an NTC / CMC Solid Composition The CNTs (Graphistrength® C100 from ARKEMA) were introduced into the first feed hopper of a BUSS® MDK 46 co-kneader (L / D = 11) with low molecular weight CarboxyMethyl Cellulose (CMC) 3033327 (grade Finnfix® 2) in solid form. A 1% solution of NaOH in demineralised water was injected at 30 ° C into the 1st zone of the co-kneader.
    [0023] The temperature setpoints and the flow rate within the co-kneader are as follows: Zone 1: 30 ° C., Zone 2: 30 ° C., Screw: 30 ° C., Flow rate: 15 kg / h. At the exit of the die, the cutting of the granules of the composition was carried out dry. A solid composition in the form of granules was obtained which can be dried in an oven at 80 ° C for 6 hours to remove water. The solid final composition in the form of granules contains 45% by weight of carbon nanotubes, 53% by weight of CMC and 2% by weight of Nat. The dried granules are packaged in an airtight container to prevent the water recovery during storage. transport to the use of the composition. EXAMPLE 2 Preparation of a 20% NTC Solid Composition NTC (Graphistrength® C100 from ARKEMA) was introduced into the first feed hopper of a BUSS® MDK 46 co-kneader (L / D = 11). ).
    [0024] A polyether polycarboxylate (PCE) in aqueous solution (Ethacryl® HF grade from Coatex) was premixed with 40% of a solution of the soluble lignosulphonate (LS) fraction neutralized with 2% NaOH by mass. This premix is composed by weight of 20% PCE, 20% LS and 1% NaOH. This liquid mixture was injected at 30 ° C into the 1st zone of the co-kneader.
    [0025] The temperature setpoints and co-kneader flow rate are as follows: Zone 1: 30 ° C, Zone 2: 30 ° C, Screw: 30 ° C, Flow rate: 15 kg / h. At the exit of the die, the cutting of the granules of the composition was carried out dry. The final composition, in the form of a moist solid, comprises 20% by weight of carbon nanotubes, 16% PCE, 16% LS and about 1% of Nat 3033327. The granules were packaged in an airtight container to avoid the loss of water. water during storage.
    权利要求:
    Claims (11)
    [0001]
    REVENDICATIONS1. Solid composition comprising from 5 to 60% by weight of carbon nanofillers dispersed in at least one water-soluble polymer in the presence of at least one cationic component chosen from alkali or alkaline earth metal cations and ammonium ions.
    [0002]
    2. Composition according to claim 1 characterized in that it comprises from 18% to 50% by weight of carbon nanofillers, preferably from 40% to 50% by weight of carbon nanofillers.
    [0003]
    3. Composition according to claim 1 or 2 characterized in that the carbon nanofillers are carbon nanotubes, graphene, or a mixture of CNT and graphene in all proportions.
    [0004]
    4. Composition according to any one of the preceding claims, characterized in that the water-soluble polymer is chosen from polysaccharides; modified polysaccharides such as modified celluloses; polyethers such as alkylene polyoxides or polyalkylene glycols; lignosulfonates; polyacrylates; products based on polycarboxylic acids, especially polyether polycarboxylates or copolymers thereof; naphthalene sulfonates and their derivatives; and their corresponding aqueous solutions.
    [0005]
    5. Composition according to any one of the preceding claims, characterized in that the water-soluble polymer is chosen from modified celluloses, in particular carboxymethylcellulose (CMC), lignosulphonates, polyether polycarboxylates or their copolymers, naphthalene sulphonates and their derivatives. , and their corresponding aqueous solutions.
    [0006]
    6. Composition according to any one of the preceding claims, characterized in that it comprises from 0.05% to 50% by weight, preferably from 0.05% to 10% by weight of cationic component. 3033327 16
    [0007]
    7. Use of the composition according to any one of claims 1 to 6 for the preparation of a lead battery electrode formulation. 5
    [0008]
    8. Lead battery electrode obtainable from a composition according to any one of claims 1 to 6.
    [0009]
    9. Electrode according to claim 8 characterized in that it is an anode. 10
    [0010]
    10. Electrode according to claim 8 characterized in that it is a cathode.
    [0011]
    11. Lead battery comprising at least one electrode according to any one of claims 8 to 10.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2012177869A2|2011-06-23|2012-12-27|Designed Nanotubes, LLC|Lead-acid battery formulations containing discrete carbon nanotubes|
    US20130264524A1|2012-04-05|2013-10-10|Kang-Yu LIU|Electrode and fabrication method thereof|
    US20140030590A1|2012-07-25|2014-01-30|Mingchao Wang|Solvent-free process based graphene electrode for energy storage devices|
    FR2914634B1|2007-04-06|2011-08-05|Arkema France|PROCESS FOR PRODUCING CARBON NANOTUBES FROM RENEWABLE RAW MATERIALS|
    FR2937324B1|2008-10-22|2012-03-16|Arkema France|PROCESS FOR THE PREPARATION OF A COMPOSITE MATERIAL BASED ON NANOTUBES, IN PARTICULAR CARBON|
    CN101877402B|2009-09-18|2012-07-25|华南师范大学|Negative plate of storage battery and manufacturing method thereof|
    FR2957910B1|2010-03-23|2012-05-11|Arkema France|MASTER MIXTURE OF CARBON NANOTUBES FOR LIQUID FORMULATIONS, PARTICULARLY IN LI-ION BATTERIES|
    FR2959231B1|2010-04-22|2012-04-20|Arkema France|THERMOPLASTIC AND / OR ELASTOMERIC COMPOSITE MATERIAL BASED ON CARBON NANOTUBES AND GRAPHICS|
    US9413001B2|2011-07-20|2016-08-09|Bar Ilan University|Functionalized carbon nanotube composite|
    CN105074970B|2013-01-25|2019-05-03|阿科玛法国公司|Method for manufacturing electrode paste|
    EP2973777A1|2013-03-14|2016-01-20|Vulcan Automotive Industries Ltd.|Process for obtaining mixtures of carbon nanotubes in solid or viscous matrices|FR3076827A1|2018-01-12|2019-07-19|Arkema France|AGGLOMERATED SOLID MATTER OF CARBON NANOTUBES DESAGREGES.|
    CN108736004A|2018-05-31|2018-11-02|深圳市瑞达电源有限公司|A kind of anode diachylon for lead-acid accumulator|
    CN113437255A|2021-05-26|2021-09-24|浙江南都电源动力股份有限公司|Low-temperature negative pole piece and preparation method thereof|
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    2016-09-09| PLSC| Search report ready|Effective date: 20160909 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1551843A|FR3033327B1|2015-03-05|2015-03-05|SOLID COMPOSITION OF CARBON NANOCHARGES FOR THE FORMULATIONS USED IN LEAD BATTERIES.|
    FR1551843|2015-03-05|FR1551843A| FR3033327B1|2015-03-05|2015-03-05|SOLID COMPOSITION OF CARBON NANOCHARGES FOR THE FORMULATIONS USED IN LEAD BATTERIES.|
    KR1020177025341A| KR20170122766A|2015-03-05|2016-03-04|Solid composition of carbon nanofillers for formulations used in lead batteries|
    JP2017545620A| JP2018508633A|2015-03-05|2016-03-04|Solid composition of carbon nanofillers for formulations used in lead batteries|
    US15/554,453| US20180047989A1|2015-03-05|2016-03-04|Solid composition of carbon nanofillers for formulations used in lead batteries|
    EP16714480.7A| EP3265511A1|2015-03-05|2016-03-04|Solid composition of carbon nanofillers for formulations used in lead batteries|
    PCT/FR2016/050502| WO2016139434A1|2015-03-05|2016-03-04|Solid composition of carbon nanofillers for formulations used in lead batteries|
    CN201680013570.1A| CN107408675A|2015-03-05|2016-03-04|For the solid composite of the carbon Nano filling of formulation used in lead battery|
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