EP1515807A4 - Nanoreseaux de nanoparticules inorganiques et de polymeres conducteurs (cpin), procede de fabrication, et batterie comprenant des nanoreseaux cpin - Google Patents

Nanoreseaux de nanoparticules inorganiques et de polymeres conducteurs (cpin), procede de fabrication, et batterie comprenant des nanoreseaux cpin

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Publication number
EP1515807A4
EP1515807A4 EP03724453A EP03724453A EP1515807A4 EP 1515807 A4 EP1515807 A4 EP 1515807A4 EP 03724453 A EP03724453 A EP 03724453A EP 03724453 A EP03724453 A EP 03724453A EP 1515807 A4 EP1515807 A4 EP 1515807A4
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Prior art keywords
nanoparticles
nanoparticle
compound
nanoarrays
molecule
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German (de)
English (en)
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EP1515807A1 (fr
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Daniel Buttry
John M Pope
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Blue Sky Group Inc
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Blue Sky Group Inc
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    • 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
    • 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
    • H01M10/058—Construction or manufacture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/013—Additives applied to the surface of polymers or polymer particles
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0472—Vertically superposed cells with vertically disposed plates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This invention relates to nanoparticles and nanoparticle composites and in particular to functionalized nanoparticles and nanoarrays and the use of the nanoparticles and functionalized nanoparticles.
  • a nanoparticle is a particle of a compound having a diameter less than 100 nm.
  • Nanoparticles have been used in various ways due to their high surface area and other features in medicine and material science. In the prior art the formation and subsequent handling of the nanoparticles has been problematic. In some instances the chemical compounds which make up the nanoparticle do not readily lend to the formation of aggregate particles of ⁇ lOOnm. In other instances the resulting nanoparticle can be readily made, however, the formed nanoparticle cannot be fully utilized due to the properties of the nanoparticle.
  • the formation of Iron based nanoparticles is accomplished through laser ablation to form particles below lOOnm in diameter. However, the Iron nanoparticles have a large surface area and are highly reactive. These particles must be kept extremely dry and out of the presence of oxygen due to being pyrophoric.
  • the nanoparticle during or after formation is connected/bound to another compound which provides the nanoparticle with stability in that the nanoparticle is nonreactive in the environment, and changes the nanoparticles chemical, physical, mechanical or electrical properties.
  • the nanoparticle is capped with the other compound.
  • the term capped should be understood to include the chemical bonding of one or a plurality of molecules or compounds to the nanoparticle's surface.
  • this capping and other compound also functionalizes the nanoparticle.
  • the functionalization may be for the connection of the nanoparticle to yet other compounds or materials to provide the nanoparticle with another or enhanced physical, chemical, mechanical or electrical property.
  • the nanoparticle By functionalizing the nanoparticle through the capping, the nanoparticle may be handled with relative ease, stored and inserted, connected or bound to other compounds or components.
  • One such functionalized nanoparticle is of nanoparticles of inorganic Li + insertion compounds with an oligomeric chain of derivatives of polythiophene type of compound attached during or after formation.
  • the capped nanoparticle exhibits handling and insertion properties.
  • This type of nanoparticle may also be inserted into a array/matrix of a conducting matrix to form an electrochemical composite.
  • This electronic array in turn utilizes the enhanced properties of the nanoparticle in order to provide desired electrochemical properties.
  • the nanoparticle provides a degree of self assembly to the substrate, composite or array. This self assembly is accomplished via methods and structure described herein.
  • Such a formed/assembled electrically conductive substrate, composite or array may be used in the formation of a battery anode and/or cathode.
  • CPIN nanoarrays self-assembling conducting polymer-inorganic nanoparticle nanoarrays
  • These CPIN nanoarrays are comprised of nanoparticles of inorganic Li + insertion compounds that are "wired” together with oligomeric chains of derivatives of polythiophene.
  • These nanoarrays have extremely high specific energy and specific power due to the unique structural characteristics that derive from the nanoarray.
  • the use of nanoparticles in CPIN nanoarrays obviates many of the undesirable characteristics of the bulk inorganic Li + insertion compounds.
  • the particles can be capped using capping agents designed to allow, for example, their incorporation into structured nanoarrays.
  • the capped particles can be incorporated into CPIN nanoarrays using a matrix material comprised of, for example, polythiophene oligomeric chains that have been synthesized to bear capping groups and pendent groups suitable for accommodating Li + .
  • a range of combinations of inorganic nanoparticles and/or CP oligomers are possible.
  • the resulting nanoarrays are electrochemically characterized, especially with respect to the reversibility of Li + insertion and expulsion, the potential that prevails during charge and discharge and the current densities that can be attained.
  • the nanoscopic nature of these materials shows electrochemical consequences (e.g. unusual kinetics).
  • Various methods are used to characterize the structural, compositional and electrical properties of the CPIN nanoarrays, especially with respect to how these properties are influenced by the nanoscopic structure. The observed electrochemical behavior is correlated with the structural, compositional and electrical properties of the CPIN nanoarrays.
  • Lithium secondary batteries have extremely high theoretical specific energy and power. However, these properties have yet to be practically achieved, especially on the cathode side. This is primarily because the electrochemical characteristics of the cathodes in these batteries are limited by several unattractive properties of the compounds used in them. For example, a very common problem with these compounds is that they exhibit substantial volumetric and/or structural changes during repeated Li + insertion and expulsion, with these changes often being irreversible. This can lead, among other things, to loss of electrical connectivity within the cathode resulting in loss of capacity, a phenomenon often called fade. Further, the degree of charging or discharging of such compounds is often purposefully limited to avoid such changes, resulting in specific energies that are well below theoretical values.
  • the Jahn-Teller distortion that occurs during reduction of manganese oxide is a classic example of a redox-driven structural change.
  • a related example is the redox-driven transition to the (undesirable) spinel structure that occurs in several manganese oxides, even those that have been purposefully prepared to have different (and more desirable) initial structures.
  • a final example is given by the fact that crystalline vanadium pentoxide can be reversibly reduced by one- electron, but not by more, unlike the amorphous xerogel and aerogel materials.
  • Binders such as poly(vinylidene fluoride), are often added to address these and other mechanical issues. However, this is undesirable because it leads to a consequent reduction in the specific energy for the cathode.
  • a second problem with the compounds used in cathodes is that they often have relatively poor electronic conductivities. This is especially true for manganese oxides, materials that are currently receiving intense scrutiny as potential cathode materials. Because of this, carbon is added to enhance the conductivity, which also leads to a reduction in specific energy.
  • a third problem with some cathode materials is that Li + diffusion rates within the material are quite low, thereby limiting the specific power that can be achieved when bulk materials are used to form the cathode. The benefit of the issues described above is that several of the materials that (in theory) have attractive redox and Li + insertion properties exhibit sub-par performance when they are used as bulk materials, especially on repeated cycling.
  • Nanoscopic arrays of nanoparticles of capped inorganic Li + insertion compounds can be produced, to embed them in matrices containing conducting polymers and or oligomers.
  • Another aspect of the present invention is to characterize the relationship between the details of their structures, composition and electrical properties and their electrochemical behavior.
  • the use of nanoscopic particles leads to several benefits. These include: Nanoscopic particles have critical nucleation radii (CNR) that are larger than the particle diameter. Structural transitions to thermodynamic sink structures (e.g. reversion of various manganese oxides to spinel) can only occur if the particle radius is larger than the critical nucleation radius for that phase. It is possible to eliminate such transitions by using nanoparticles with CNRs larger than the particle radius. This "freezes" the particle into its initially formed state, which may be amorphous or a metastable (or stable) crystalline state.
  • CNR critical nucleation radii
  • the fraction of Mn(IV) ions at the surface will be 0.5, while for a 10 nm particle it will be 0.05. Further, for a 10 nm particle the fraction of Mn(IV) ions within next-nearest neighbor distance of the surface is 0.75.
  • a significant fraction of the lattice negative charge for nanoparticles during discharge is either at or very near the surface. This reduces the need for bulk diffusion of Li + , greatly increasing the charge and discharge rate of the cathode. This also reduces the volumetric changes and lattice stresses caused by repeated Li + insertion and expulsion.
  • Li + diffusion distances will be significantly reduced.
  • the time required for Li + to diffuse a distance equal to the particle radius is 2.5 x 10 ⁇ 3 s.
  • Li + diffusion within the particle to compensate reduction of non-surface Mn sites is not a significant kinetic barrier during cycling.
  • the surface functionality can prevent agglomeration of the nanoparticles, inhibit nanoparticle dissolution and allow the use of rational self- assembly processes when assembling the cathode.
  • Prevention of agglomeration by capping for V2O5 will be described below. Capping will passivate the nanoparticle toward dissolution and other chemical processes. Dissolution is a common problem for various manganese oxides.
  • capping provides a chemical "handle" that can be used to direct the self- organization of the CPIN nanoarray (e.g. in a self-assembly process). This will be discussed in considerable detail below.
  • Wiring the nanoparticles can obviate the need to add carbon filler and ensure good electronic addressability of all of the nanoparticles in the nanoarray. This reduces both the ohmic losses across the cathode and the loss of contact that often results in capacity fade for cathodes. Wiring is considered herein as binding of the nanoparticle to a substrate matrix, composite and/or other nanoparticles electrically.
  • Nanoscopic particles surrounded by a relatively elastic conducting polymer matrix are sufficiently resilient to reversibly accommodate the volumetric changes that occur during Li + insertion and expulsion. This is important to developing cathodes than can reversibly accommodate large amounts of Li + .
  • Fig. 1 shows a nanoparticle reactor
  • Fig. 2 shows a photograph of uncapped and capped V205 nanoparticles
  • Fig. 3 shows a bridged system of nanoparticles
  • Fig. 4 shows one embodiment of a synthetic route for a capping compound for a nanoparticle
  • Fig. 5 shows a second embodiment of a synthetic route for a capping compound for a nanoparticle
  • Fig. 6 shows a third embodiment of a synthetic route for a capping compound for a nanoparticle
  • Fig. 7 shows a NMR spectra of a series of Li x V2 ⁇ xerogel samples at various stages of Li + insertion
  • Fig. 8 shows a self assembling matrix system
  • Fig. 9 shows a functionalized nanoparticle.
  • nanoparticles are envisioned.
  • One particularly useful method of manufacture is via formation in a CVD reactor.
  • the precursors for the nanoparticles may include several compounds which react or bind within the reactor.
  • the apparatus and method using a sole precursor for production is discussed below.
  • a method of manufacturing the nanoparticles is described but is not meant to limit the envisioned methods of producing the nanoparticles.
  • a unary precursor nanoparticle process reactor is described by its operation.
  • typical reagents may include but are not limited to the following examples: vanadium oxytriethoxide, aluminum isopropoxide, titanium (IV) isopropoxide, tantalum (V) ethoxide.
  • the particle precursor material 5 is placed in the precursor vessel 2. Typically these materials are liquids however solids may be used also.
  • the precursor vessel may be heated or cooled to control the vapor pressure of the precursor as appropriate for the precursor in use with a heating element 6. Importantly this allows, via a mass flow controller 3, for metered isobaric delivery of the precursor into the reactor tube 4. Additionally, metering of the precursor by the mass flow controller controls the flow rate of the precursor which, in turn, determines the residence time of the precursor in the heated reactor tube. The residence time is important as this is the time the precursor has to react in the heated zone 7 of the reactor tube.
  • the residence time required for decomposition is dependant on the decomposition kinetics of each precursor.
  • the precursor vapor thus is delivered into the top of the reactor tube.
  • the reactor tube is heated with multi- zone heating elements 8 to allow precise control of the temperature regime along the length of the tube.
  • the temperature profile of the tube is chosen to affect decomposition of the precursor within the tube. Temperature is typically in the range 300-600 degrees centigrade. Process pressure is carefully controlled and monitored continuously. The pressure is typically maintained in an isobaric manner within a range from 1-50 torr. Process pressure control is achieved by means of an inline throttling valve 9 upstream of the vacuum pump 10. This valve is slaved to a pressure gauge/pressure controller combination 12. Process temperature, pressure and precursor flow rate together control the desired size, morphology, dispersity and extent of agglomerization of the material obtained. Homogenous nucleation of particle growth during precursor decomposition is also realized by the careful control of these parameters.
  • a sintered glass disc 11 in the particle trap 13 sequesters the nanoparticulate material.
  • particles Prior to capture, if desired, particles may be in-flight capped by introduction of the vapor of a capping agent. The amount of cap vapor is controlled in a fashion comparable to the particle precursor reagent.
  • the collected particles may be recovered directly from the trap. Alternatively, three isolating valves 14, 15, 16 may be closed and the material within the trap handled appropriately if anaerobic handling conditions are required.
  • Nanoparticles in the 10 to 50 nm size range have been produced.
  • Figure 2 shows TEM images of V2O5 nanoparticles produced via homogeneous nucleation in a CVD reactor. The precursor for these nanoparticles, VO(OCH2CH3)3, was reacted with O2 and H 2 0 at low pressure and 400 °C under carefully controlled mass flow conditions to give the nanoparticles shown on the left.
  • the CVD reactor can be run under a variety of conditions to give samples of varying properties.
  • the image on the right of Figure 2 shows nanoparticles that have been capped using SiCl(CHs)3. This capping was done after the nanoparticles were produced via simple exposure of the nanoparticles to the capping reagent in dry toluene.
  • nanoparticles have been extensively characterized using FTIR, UV-VTS, TEM, electrochemistry and elemental analysis. As can be seen, capping stabilizes the nanoparticles toward agglomeration. Other methods and apparatuses of production are also envisioned for the nanoparticles being produced.
  • a schematic of a surface of a typical capped nanoparticle is shown in Fig. 9. The surface has several molecules or compounds bound to it to functionalize the nanoparticle.
  • inorganic oxide nanoparticles are produced using the CVD approach, including manganese oxide, vanadium oxide, nickel oxide and cobalt oxide.
  • the third and fourth can be prepared using organometallic precursors, such as the acetates and 2,4-pentanedionates. It is also possible in this reactor to produce mixed metal nanoparticles, given the attractive properties for mixed systems.
  • Size control of the nanoparticles is readily achieved using temperature and mass flow rate control, both of which are incorporated into the CVD reactor. Note that CVD is usually used for heterogeneous thin film growth. However, due to the control, homogeneous nucleation within the reactor is a possibility.
  • Inorganic oxide nanoparticles using solution phase approaches are also produced.
  • sol-gel method for producing ZnO nanoparticles An attraction of this method is that it gives nanoparticles that are weakly capped with poly(vinylpyrrolidone) (PVP).
  • PVP poly(vinylpyrrolidone)
  • This amide-based capping agent is not strongly bound and is easily displaced by other more strongly coordinating capping agents.
  • this approach can be used to produce nanoparticles that are easily handled, and can be capped with other reagents during the nanoarray assembly.
  • solution phase approaches are available for producing insertion oxides for Li + . In many cases, they produce nanoparticulate materials. Both CVD and solution phase production methods give us the widest possible access to the various types of inorganic oxides that are of use.
  • synthesis of the thiophene oligomers is important.
  • the oligomers bear capping groups at both ends and some have pendent groups designed to facilitate Li + diffusion within the material.
  • Bridges are produced that will allow capping of the nanoparticles such that they form 3D structures with high electronic and ionic conductivities and high capacity toward Li + insertion.
  • the structure in Fig. 3 shows an example of a simple bridged system. In this case, a sexithiophene molecular "wire" is used to electronically bridge the nanoparticles while the capping is achieved using the same type of silane coupling chemistry already employed (as in Fig. 2). Other capping chemistries are available.
  • bridge serves several important purposes including direction of the self-assembly of the nanoarray, stabilization of the nanoparticles and maintenance of the electronic conductivity of the nanoarray.
  • Other bridges to be described below also have structures designed to facilitate Li + accommodation, and to produce capping that is either irreversible (as for the silane system) or moderately reversible.
  • the sexithiophene system is focused on for several very important reasons.
  • Second, the six ring system is just large enough to stabilize the cation radical formed during p-doping of the material. Thus, it has very good stability toward repeated oxidation and storage in the p-doped state.
  • Third, the length is just sufficient for bridging between nanoparticles in the 10-50 nm size range. Also, oligomeric ring systems with 2-6 rings between metallic nanoparticles give excellent electronic coupling. A similar approach is suitable for oxide nanoparticles.
  • poly(thiophene) and its oligomers are p-doped at potentials that are in the right range (ca. 0.3-0.9 V vs. SCE) to allow them to store charge just as do the Li + insertion compounds in Li secondary battery cathode.
  • they add charge storage capacity to the material, rather than detracting from it, as is the case for carbon and elastomeric additives.
  • the first synthetic scheme shows one synthetic approach to a sexithiophene that bears pendent ether groups and has carboxylic acid (or carboxylate) terminal groups suitable for capping a wide variety of transition metal insertion oxide nanoparticles.
  • This synthesis is a combination of several methods for thiophene oligomer synthesis. These use the widely applied Stille cross coupling reaction. This route uses aldehyde end- capped oligomers. It is particularly noteworthy that the bis(ether)bithiophene is the starting material.
  • end-capped oligothiop enes have been prepared, including an aminomethyl derivative.
  • This compound may be suitable for serving as a molecular bridge for transition metal oxides that prefer hard Lewis acid donors, such as high valent Co and Ni. Also, the fact that it is unidentate allows that its binding is more reversible than that of the bidentate carboxylates. This has implications for the assembly approaches that can be used, as described below.
  • This approach relies on low temperature physical methods that produce aggregation and/or assembly of the nanoparticles. These include simple solvent evaporation, use of capillary forces and flow induced assembly. Some approaches to self-assembly of colloidal materials produce colloidal "single crystals." In many cases, control of the concentration of the nanoparticle solutions is required prior to these steps. This can be done using centrifuge-redisperse cycles or simple solvent evaporation-redispersion. We also envision using dialysis procedures using very low MW-cutoff membrane materials to produce highly concentrated nanoparticle solutions. All redispersion approaches may require that some measure of coordination from the solvent (or other intentionally added reagent) occur so as to break up interparticle interactions.
  • Coordinating solvents may be needed to disperse the nanoparticles from the agglomerated states they will be in after synthesis. This will be especially true if the nanoparticles have not been purposefully capped after synthesis.
  • Suitable solvents include THF, acetonitrile (ACN) and various amide solvents (NMP, DMF, formamide), since these are all weakly coordinating. It is important that the solvents not be too strongly coordinating, since they must be displaced by the capping groups at the ends of the sexithiophene bridges during final assembly.
  • a typical sequence of events for the "prior assembly” method would be the following.
  • the nanoparticles would be synthesized using either CVD or solution phase techniques. In both cases, they would be isolated as powders. They would then be redispersed in a weakly coordinating solvent, such as ACN, using ultrasonic irradiation to assist in dispersion if necessary.
  • An aliquot of this solution would be placed on a substrate (e.g. indium-tin oxide glass, mica or a Au thin film with a monolayer of mercaptoundecanoic acid (MUA), which presents carboxylate groups to the solution), and assembly would be allowed to take place in an atmosphere that is nearly saturated with respect to the dispersion solvent.
  • a substrate e.g. indium-tin oxide glass, mica or a Au thin film with a monolayer of mercaptoundecanoic acid (MUA), which presents carboxylate groups to the solution
  • Capping is achieved by exposure of the array to the oligomeric bridge under conditions that will not allow for wholesale dissolution of the array.
  • the array is sandwiched between its own substrate (ITO, mica or SAM-coated Au on mica) and an equally flat, chemically inert second substrate.
  • ITO indium
  • mica substrates the extreme flatness will assist in confining the array.
  • the edge of the sandwich is exposed to a solution of the bridging agent which will be dissolved in a non-coordinating solvent, such as CH2CI2, which is known to dissolve the ⁇ - ⁇ -disubstituted aldehyde sexithiophene derivative.
  • the molecular bridge is allowed to diffuse slowly into the nanoarray, but the confinement and poorly coordinating solvents may prevent dissolution. Either reversible (e.g. carboxylate) or irreversible capping (e.g. silane) can be achieved in this way.
  • the nanoarray is structurally stable, allowing examination with the characterization methods described below.
  • the ⁇ - ⁇ -disubstituted sexithiophene bridging agents are combined with the nanoparticles in solution.
  • this combination can be conducted.
  • the nanoparticle solution is added slowly to a solution of the molecular bridge. This produces solutions in which the nanoparticles are surrounded by a large number of bridging agents. The number is controllable based on the relative stoichiometries of the bridges and the nanoparticles.
  • the nanoarray allows for stabilization of the nanoparticles via capping.
  • the presence of the bridges will cause the system to establish interparticle distances that are optimized with regard to the length of the bridges.
  • the initial physical processes that bring the nanoparticles into close proximity are capillary forces that are essentially the same as those described above.
  • the ⁇ - ⁇ -disubstituted molecular bridges connect the particles. This establishes the interparticle distance and locks the nanoarray into this structure.
  • the second limiting case in this strategy involves adding the molecular bridge solution to a solution of the nanoparticles.
  • both ends of a given oligomer will be immediately attached to nanoparticles, producing a dimeric species.
  • Further addition ultimately produces trimers, tetramers, etc. until large aggregates are formed. At some point, these will not be stable in solution, and precipitation occurs.
  • Such a sequence may not give high quality nanoarrays with long range order. However, order may not be a requirement for desirable electrochemical behavior with respect to Li + insertion. Having produced CPIN nanoarrays via the methods described above, we proceed to characterize them using several techniques available.
  • a typical self-assembling array is shown in Fig. 8 when the polymers are dispersed with the nanoparticles and the self assemble into the array by the polymer interacting with the nanoparticles.
  • the polymers also bind to an electrically conducting substrate.
  • This method is based on the use of layer-by-layer methods to produce nanoarrays of Au or Ag nanoparticles using sulfur adsorption or Ti ⁇ 2 embedded in a polymeric material.
  • a typical protocol is to first prepare a suitable substrate, such as MUA adsorbed on Au (on mica, Si or glass). This substrate is exposed to a dispersion of the uncapped nanoparticles in a weakly coordinating solvent. This leads to adsorption of a first layer of nanoparticles, producing a 2D nanoarray. This is then immersed in a solution of an ⁇ - ⁇ -disubstituted sexithiophene, which adsorbs onto the nanoparticles, producing a surface that bears the functional group for that capping agent. This surface is then exposed to the nanoparticle solution again, yielding adsorption of a second layer of nanoparticles. This process can be repeated many times to build up multilayer CPIN nanoarrays.
  • ac impedance methods can be very fruitfully applied to develop an understanding of both the ionic and electronic conductivity of thin film samples.
  • Specific electrochemical techniques to be used include cyclic voltammetry for survey work; charge-discharge curves for quantitative assays of charge capacity, discharge potential, and long term reversibility; and ac impedance for characterization of electronic and ionic conductivity.
  • a second effect that may be observed for nanoarrays comprised on extremely small nanoparticles is a type of Coulomb trapping effect. This effect can result when the small size of a particle leads to discrete steps in its potential due to capacitive charging effects. In ensembles, it is only observed when the nanoparticle size is extremely monodisperse. The CPIN nanoarray systems are examined for such effects.
  • EQCM EQCM
  • One of the EQCM experiments is the dissection of Li + , anion and solvent transport via use of isotopically substituted species, such as 6 Li + vs. 7 Li + , and deuterated vs. protiated solvents. Measurements of solvent swelling will be important to understanding how the mechanical properties of the polymer matrix influence the accommodation of the reversible volumetric changes that accompany Li + insertion and expulsion, since the swelling provides an indirect measure of the film's mechanical properties.
  • Li + insertion compounds such as V2O5, using 6 Li, 7 Li and 51 V NMR.
  • This tool allows for facile compositional assessments, study of the structural aspects of Li + insertion (e.g. are there multiple sites at which Li + interacts with the nanoparticles?), and Li + mobility.
  • a unique capability of this method is its ability to probe the distances between electronic spins (either on nanoparticles within the nanoarrays or on the conducting polymer chains) and the various nuclei being examined. Thus, it is ideally suited to the systems we describe here because the length scale over which such interactions are relevant matches the range of the feature sizes of the CPIN nanoarrays.
  • the broader band is due to paramagnetic broadening of some of the charge compensating Li + species. These are likely Li + that have intercalated into the material and are in close proximity to the paramagnetic vanadium (IV) sites. It is possible to use such data to calculate the distances between the Li + species and the paramagnetic sites. This helps us understand if the Li + species are inside of the inorganic nanoparticles or outside, and under what conditions these two states occur. Thus, use of such data helps us understand how the details of local structure influence the Li + in these CPI ⁇ nanoarrays.
  • the foregoing disclosure has been set forth merely to illustrate the invention and is not intended to be limiting. Since modifications of the disclosed embodiments incorporating the spirit and substance of the invention may occur to persons skilled in the art, the invention should be construed to include everything within the scope of the appended claims and equivalents thereof.

Abstract

L'invention concerne un nanoréseau de nanoparticules inorganiques et de polymères conducteurs. Les nanoparticules sont formées et coiffées, ce qui permet d'améliorer leurs propriétés et de les manipuler plus facilement. Le coiffage peut s'effectuer lorsque les nanoparticules sont formées, et permet de fonctionnaliser celles-ci. Les nanoparticules sont alors liées à des polymères conducteurs de manière à obtenir une matrice électroconductrice qui peut être à son tour électriquement connectée à un substrat pour former une anode ou une cathode pour une batterie au lithium. Les nanoparticules sont électriquement reliées les unes aux autres dans la matrice à l'aide de l'agent de coiffage et/ou du polymère conducteur. Le polymère conducteur permet une insertion de Li+ répétée dans l'anode ou la cathode d'une batterie.
EP03724453A 2002-05-06 2003-05-06 Nanoreseaux de nanoparticules inorganiques et de polymeres conducteurs (cpin), procede de fabrication, et batterie comprenant des nanoreseaux cpin Withdrawn EP1515807A4 (fr)

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US6344272B1 (en) * 1997-03-12 2002-02-05 Wm. Marsh Rice University Metal nanoshells

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