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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
  • H01M4/624—Electric conductive fillers
• • 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
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  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
  • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
• • 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
  • H01B1/121—Charge-transfer complexes
• • 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
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
• • 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
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/134—Electrodes based on metals, Si or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
  • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/386—Silicon or alloys based on silicon
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/10—Definition of the polymer structure
  • C08G2261/12—Copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
  • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
  • C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/50—Physical properties
  • C08G2261/51—Charge transport
  • C08G2261/516—Charge transport ion-conductive
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
• • 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 generally to lithium ion batteries, and more specifically to an improved polymeric binder for forming silicon electrodes resulting in battery electrodes of increased charge density.
• Lithium-ion batteries are a type of rechargeable battery in which lithium ions move between the negative and positive electrode.
• the lithium ion moves through an electrolyte from the negative to the positive during discharge, and in reverse, from the positive to the negative, during recharge.
• the negative electrode is made of graphite, which material is particularly preferred due to its stability during charge and discharge cycles as it forms solid electrolyte interface (SEI) layers with very small volume change.
• SEI solid electrolyte interface
• Lithium ion batteries and finding ever increasing acceptance as power sources for portable electronics such as mobile phones and laptop computers that require high energy density and long lifetime. Such batteries are also finding application as power sources for automobiles, where recharge cycle capability and energy density arc key requirements.
• research is being conducted in the area of improved electrolytes, and improved electrodes. High- capacity electrodes for lithium-ion batteries have yet to be developed in order to meet the 40- rnile plug-in hybrid electric vehicle energy density needs that are currently targeted.
• One approach is to replace graphite as the negative electrode with silicon.
• graphite electrodes are rated at 372 mAh/g (milliamp hours per gram) at LiCe, while silicon electrodes are rated more than tenfold better at 4,200 mAh/g at Li 4.4Si.
• numerous issues prevent this material from being used as a negative electrode material in lithium-ion batteries.
• Full capacity cycling of Si results in significant capacity fade due to a large volume change during Li insertion (lithiation) and removal (de-lithiatkm). This volumetric change during reasonable cycling rates induces significant amounts of stress in micron size particles, causing the particles to fracture.
• an electrode made with micron-size Si particles has to be cycled in a limited voltage range to minimize volume change.
• a new class of binder materials has been designed and synthesized to be used in the fabrication of silicon containing electrodes.
• These new binders which become conductive on first charge, provide improved binding force to the Si surface to help maintain good electronic connectivity throughout the electrode, to thus promote the ilow of current through the electrode.
• the electrodes made with these binders have significantly improved the cycling capability of Si, due in part to their elasticity and ability to bind with the silicon particles used in the fabrication of the electrode.
• a novel class of conductive polymers can be used as conductive binders for the anode electrode.
• These polymers include poiy 9,9-dioctylfluorene and 9-fluorcnonc copolymer.
• the polyfluorene polymer can be reduced around 1.0 V (vs. lithium metal potential) and becomes very conductive from 0 - 1.0 V. Since negative electrodes (such as Si) operate within a 0 - 1.0 V window, this allows polyiluorcnc to be used as an anode binder in the lithium ion batter) ' to provide both mechanical binding and electric pathways.
• As a unique feature of this polymer by modifying the side chain of the poiyfluorene conductive polymer with functional groups such as -COOH that will bond with Si nanocrystals, significantly improved adhesion can be realized.
• Figure 1 depicts a generic chemical formula of a conductive polymer binder according to an embodiment of the present invention.
• Figure 3 is a plot of Coulombic Efficiency (%) vs. Cycle Number for the same Si anode/conductive binder electrode of Figure 2.
• Figure 4 shows the voltage profile of the electrode of Figure 2 in the first several cycles of lithium insertion and removal.
• Figure 5 shows the de-lithiation performance of the same electrode at different charge- rates.
• Figure 6 is a plot of Si electrode cycling behavior at fixed capacity for the electrode of Figure 2. When the iithiation is limited to a selected capacity, the de-lithiation capacities are stable in 100 cycles as shown.
• Figure 7 is a plot of cycling results for a PFFOMB (poly(9,9-dioctylfluorene-co- fSuorenone-co-m ⁇ thylbenzoic acid)) binder used in combination with an electrolyte comprising LiPF 6 in EC/DEC + 10% FEC.
• PFFOMB poly(9,9-dioctylfluorene-co- fSuorenone-co-m ⁇ thylbenzoic acid
• the conductive polymers developed herein act as a binder for the silicon particles used for the construction of the negative anode. They are mixed with the silicon nano sized silicon parties in a slurry process, then coated on a substrate such as copper or aluminum and thereafter allowed to dry to form the film electrode.
• the silicon particles can range from micron to nano size, the use of nano sized particles is preferred as such results in an electrode material that can better accommodate volume changes.
• a fabrication method for the synthesis of one embodiment of the binder polymer of this invention is as set forth below. First presented is a means for preparing one of the monomers used in polymer formation, i.e. 2,5-dibromo ⁇ l ,4-benzenedicarboxylic acid, a reaction scheme for preparing this monomer illustrated at paragraph [0020], immediately below.
• R5 and Ke can be any combination of H, COOH and COOCtI 3 .
• Another variation is to adjust the number of COOH groups by copolyracrizing x monomer into the main chains as illustrated in the formula shown below.
• the ratio of x:x' By adjusting the ratio of x:x', the number of -COOH groups can be controlled without changing the electronic properties of the conductive binders. Exemplary of such a composition is as illustrated below by the following formula. [0030]
• Ri and R 2 can be (CH 2J n CI-! 3, n ::: 0 - 8.
• R5 and R 6 can be any combination of H, COOH and COOCtI 3 ; arid the 'X x'" unit is lluorene with either alkyl or alkylcarboxylic acid at the 9, 9 'positions; the "y" unit is fluorenone,
• the H positions of the back bone of fluorenon and lluorene also can be substituted with functional groups such as COOH, F, Cl, Br, SO 3 H, etc,
• R ⁇ and R* can be any combination of H, COOH and COOCHj.
• n is a flexible alkyl or polyethylene portion.
• This flexible unit (n) can be one or many of -CH 2 units depending upon the requirements for a particular alloy system, or could be other types of liner units depending on the ease of synthesis.
• Both x, x', y and z units could be one or many fluorene or fluorenone units.
• Ri-Rt units
• the Ri-Rt, units could be either one of the choices, and it is not necessary they be all the same in a polymer chain. Increasing the length of the side chains may also have an effect on the flexibility of the polymer binder. Therefore, the number of units in R 1 - Rf, is also subject to change during an optimization process. One may change the number of units of the Ri-R(I, and look for improved cell cycling performance as indication of optimization.
• the binder may cover (that is, over-coat) all the active materials at higher binder loadings. Such over-coverage will modify the interface stability and impedance. Varying the number of units in Ri-Re will play a significant role in optimizing the charge transfer impedance at the interface.
• PFFOM B ( ⁇ oly(9,9 ⁇ dioctyl fluorene-co-fluorcnone-co-rnelhylben/.oic acid)
• the conductive polymers can be mixed with the silicon particles, and coated onto a substrate such as copper and allowed to dry to form the electrode material.
• a substrate such as copper and allowed to dry to form the electrode material.
• An advantage of the use of these conductive polymers of the present invention is that they are easily compatible with current slurry processes for making electrodes, thus requiring no special steps or equipment,
• a Branson 450 sonicator equipped with a solid horn was used, The sonication power was set at 70%. A continuous sequence of 10 second pulses followed by 30 second rests was used. The sonic dispersion process took about 30 min. All of the mixing processes were performed in Ar- tilled glove boxes,
• slurries of AB PVDF (acetylene black/poiyvinyiidcne fluoride) at 0,2:1 ratios by weight were made by dissolving 5g of PVDF in to 95 g of NMP to make a 5% PVDF in NMP solution. Proper amounts of AB was dispersed in the PVDF solution to meet the desired AB: PVDF ratios.
• the Branson 450 sonicator equipped with a solid horn was used. The sonication power was set at 70"/.). A continuous sequence of 10 s pulses followed by 30 s rests was used. The sonic dispersion process took ca. 30 min. All of the mixing processes were performed in Ar-filled to glove boxes.
• All electrode laminates were cast onto a 20 ⁇ m thick battery-grade Cu sheet using a Mitutoyo doctor blade and a Yoshimitsu Seiki vacuum drawdown coater to roughly the same loading per unit area of active material.
• the films and laminates were first dried under infrared lamps for 1 h until most of the solvent was evaporated and they appeared dried, The films and laminates were further dried at 120 0 C under 1 Q ⁇ ⁇ Torr dynamic vacuum for 24 h.
• the film and laminate thicknesses were measured with a Mitutoyo micrometer with an accuracy of ⁇ 1 ⁇ m, The typical thickness of film is about 20 ⁇ rn.
• the electrodes were compressed io 35% porosity before coin cell assembly using a calender machine from International Rolling Mill equipped with a continuously adjustable gap.
• Coin cell assembly was performed using standard 2325 coin cell hardware.
• a 1.47 cm diameter disk was punched out from the laminate for use in the coin cell assembly as a working electrode.
• Lithium foil was used in making the counter electrode.
• the counter electrodes were cut to 1.5 cm diameter disks.
• the working electrode was placed in the center of the outer shell of the coin cell assembly and two drops of 1 M LiPFg in EC: DEC (1 :1 weight ratio) electrolyte purchased from Ferro Inc. were added to wet the electrode, A 2 cm diameter of C ⁇ lgard 2400 porous polyethylene separator was placed on top of the working electrode. Three more drops of the electrolyte were added to the separator.
• the counter electrode was placed on the top of the separator.
• the coin cell performance was evaluated in a thermal chamber at 30 0 C with a Maccor Series 4000 Batter ⁇ ' Test System.
• the cycling voltage limits were set at 1.0 V at the top of the charge and 0.01 V at the end of the discharge.
• the conductive polymers of this invention can be used as electrically conductive binders for Si nanoparticles electrodes.
• the electron withdrawing units lowering the LUMO level of the conductive polymer make it prone to reduction around 1 V against a lithium reference, and the carboxylic acid groups provide covalent bonding with OH groups on the Si surface by forming ester bonds.
• the alkyls in the main chain provide flexibility for the binder.
• Figure 2 shows the new conductive polymer binder in combination with Si nanoparticles much improving the capacity retention compared to conventional acetylene black (AB) and polyvinylidene difluride (PVDF) conductive additive and binder as a control.
• Figure 3 illustrates the improved coulornbic efficiency of the conductive binder/Si electrode of the invention compared with the conventional AB/PVDF approach.
• Figure 4 illustrates results showing very similar voltage profiles of the conductive polymer/Si electrode to the pure Si film type of electrode.
• Figure 5 plots the rate performance of the conductive polymer/Si electrode of the invention, showing good results.
• Figure 6 illustrates cycleabiiity of the silicon electrode made with the copolymer binder of the invention, which is very good at limited capacity range. There is no capacity fade in 100 cycles at 1200 mAh/g and 600 niAh/g fixed capacity cycling.

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