# Patent

## Title
Electronically conductive polymer binder for lithium-ion battery electrode

## Abstract

A family of carboxylic acid group containing fluorene/fluorenon copolymers is disclosed as binders of silicon particles in the fabrication of negative electrodes for use with lithium ion batteries. These binders enable the use of silicon as an electrode material as they significantly improve the cycle-ability of silicon by preventing electrode degradation over time. In particular, these polymers, which become conductive on first charge, bind to the silicon particles of the electrode, are flexible so as to better accommodate the expansion and contraction of the electrode during charge/discharge, and being conductive promote the flow battery current.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. application Ser. No. 13/294,885, filed Nov. 11, 2011 and entitled Electronically Conductive Polymer Binder for Lithium-Ion Battery Electrode, now issued as U.S. Pat. No. 8,852,461, which is a continuation of PCT Application No. PCT/US2010/035120, filed May 17, 2010 and entitled Electronically Conductive Polymer Binder for Lithium-Ion Battery Electrode; which claims priority to U.S. Provisional Application Ser. No. 61/179,258 filed May 18, 2009, and U.S. Provisional Application Ser. No. 61/243,076 filed Sep. 16, 2009, both entitled Electronically Conductive Polymer Binder for Lithium-Ion Battery Electrode, Liu et al. inventors; each of which applications is incorporated herein by reference as if fully set forth in their entirety.


STATEMENT OF GOVERNMENTAL SUPPORT
The invention described and claimed herein was made in part utilizing funds supplied by the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The government has certain rights in this invention.


BACKGROUND OF THE INVENTION
Field of the Invention
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.
Background of the Invention
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. Most commonly 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.
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 are key requirements. In this regard, 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-mile plug-in hybrid electric vehicle energy density needs that are currently targeted.
One approach is to replace graphite as the negative electrode with silicon. Notably graphite electrodes are rated at 372 mAh/g (milliamp hours per gram) at LiC6, while silicon electrodes are rated more than tenfold better at 4,200 mAh/g at Li4.4Si. However, 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-lithiation). This volumetric change during reasonable cycling rates induces significant amounts of stress in micron size particles, causing the particles to fracture. Thus an electrode made with micron-size Si particles has to be cycled in a limited voltage range to minimize volume change.
Decreasing the particle size to nanometer scale can be an effective means of accommodating the volume change. However, the repeated volume change during cycling can also lead to repositioning of the particles in the electrode matrix and result in particle dislocation from the conductive matrix. This dislocation of particles causes the rapid fade of the electrode capacity during cycling, even though the Si particles are not fractured. Novel nano-fabrication strategies have been used to address some of the issues seen in the Si electrode, with some degree of success. However, these processes incur significantly higher manufacturing costs, as some of the approaches are not compatible with current Li ion manufacture technology. Thus, there remains the need for a simple, efficient and cost effective means for improving the stability and cycle-ability of silicon electrodes for use in Lithium ion batteries.
SUMMARY OF INVENTION
By way of this invention, 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 flow 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.
More particularly, we have found that a novel class of conductive polymers can be used as conductive binders for the anode electrode. These polymers include poly 9,9-dioctylfluorene and 9-fluorenone 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 polyfluorene to be used as an anode binder in the lithium ion battery to provide both mechanical binding and electric pathways. As a unique feature of this polymer, by modifying the side chain of the polyfluorene conductive polymer with functional groups such as —COOH that will bond with Si nanocrystals, significantly improved adhesion can be realized.



BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing aspects and others will be readily appreciated by the skilled artisan from the following description of illustrative embodiments when read in conjunction with the accompanying drawings.
FIG. 1 depicts a generic chemical formula of a conductive polymer binder according to an embodiment of the present invention.
FIG. 2 is a plot of electrode capacity vs. cycle number for a Si anode made with the conductive binder of FIG. 1 according to one embodiment of the invention, wherein R1=R2=(CH2)7CH3, R5=COOCH3, R6=H and x=0.5, x′=0, y=0.175 and z=0.325.
FIG. 3 is a plot of Coulombic Efficiency (%) vs. Cycle Number for the same Si anode/conductive binder electrode of FIG. 2.
FIG. 4 shows the voltage profile of the electrode of FIG. 2 in the first several cycles of lithium insertion and removal.
FIG. 5 shows the de-lithiation performance of the same electrode at different charge-rates.
FIG. 6 is a plot of Si electrode cycling behavior at fixed capacity for the electrode of FIG. 2. When the lithiation is limited to a selected capacity, the de-lithiation capacities are stable in 100 cycles as shown.
FIG. 7 is a plot of cycling results for a PFFOMB (poly(9,9-dioctylfluorene-co-fluorenone-co-methylbenzoic acid)) binder used in combination with an electrolyte comprising LiPF6 in EC/DEC+10% FEC.



DETAILED DESCRIPTION
According to this invention 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. Though 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-1,4-benzenedicarboxylic acid, a reaction scheme for preparing this monomer is illustrated immediately below.




When the benzenedicarboxylic acid staring material has only one CH3 group, the reaction will end up with only one R=COOCH3 group in the final product.
A. Synthesis of Polymeric PFFO (poly(9,9-dioctylfluorene-co-fluorenone))
Exemplary of a method for forming one of the polymers of this invention is provided with respect to one embodiment, according to the reaction scheme set forth below. A mixture of 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester (0.83 g, 1.5 mmol) commercially available from Sigma-Aldrich Company, 2,7-dibromo-9-fluorenone (0.50 g, 1.5 mmol), (PPh3)4Pd(0) (0.085 g, 0.07 mmol) and several drops of aliquat 336 in a mixture of 10 mL of THF (tetrahydrofuran) and 4.5 mL of 2 M Na2CO3 solution was refluxed with vigorous stirring for 72 hours under an argon atmosphere. During the polymerization, a brownish solid precipitated out of solution. The solid was collected and purified by Soxhlet extraction with acetone as solvent for two days with a yield of 86%.




B. Synthesis of PFFOMB (poly(9,9-dioctylfluorene-co-fluorenone-co-methylbenzoic acid))
A mixture of 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester (0.80 g, 1.43 mmol), 2,7-dibromo-9-fluorenone (0.24 g, 0.72 mmol), methyl 2,5-dibromobenzoate (0.21 g, 0.72 mmol), (PPh3)4Pd(0) (0.082 g, 0.072 mmol) and several drops of Aliquat 336 in a mixture of 13 mL of THF (tetrahydrofuran) and 5 mL of 2 M Na2CO3 solution was refluxed with vigorous stirring for 72 h under an argon atmosphere. After reaction stopped, the solution was concentrated by vacuum evaporation and the polymer was precipitated from methanol. The resulting polymer was further purified by precipitating from methanol twice. The final polymer was collected by suction filtration and dried under vacuum with a yield of 87%.
C. Synthesis of PFFOBA (poly(9,9-dioctylfluorene-co-fluorenone-co-benzoic acid))
A mixture of PFFOMB (0.36 g) and KOH (2 g, 35 mmol) in 20 mL of THF and 2 mL of H2O was refluxed for 48 h under an argon atmosphere. After reaction stopped, the solution was concentrated by vacuum evaporation and polymer was precipitated from methanol. The resulting polymer was suspended in 10 mL of concentrated H2SO4 with vigorous stirring for 12 hours. The final product was filtered, washed with water and dried with a yield of 96%.




Reaction scheme for forming conductive polymer with —COOCH3 (PFFOMB) and —COOH (PFFOBA) groups on the side chains.

It has been found that the presence of —COOH groups serves to increase the bindability of the polymer to the silicon particles of the electrode. In particular, one can position carboxylic acid groups in connection with the 9th position of fluorene backbone. The below formula depicts the general structure of this type of polymer.




Wherein x=0, x′ and y=>0, and z<=1, and x′+y+z=1, R3 and R4 can be (CH2)nCOOH, n=0-8, and R5 and R6 can be any combination of H, COOH and COOCH3.

Another variation is to adjust the number of COOH groups by copolymerizing x monomer into the main chains as illustrated in the formula shown below. 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.




wherein, x, x′, y>0, and z<=1, with x+x′+y+z=1. R1 and R2 can be (CH2)nCH3, n=0-8. R3 and R4 can be (CH2)nCOOH, n=0-8. R5 and R6 can be any combination of H, COOH and COOCH3; and the “x, x′” unit is fluorene 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 fluorene also can be substituted with functional groups such as COOH, F, Cl, Br, SO3H, etc.

In still another embodiment, one can increase the flexibility of the polymer by introducing a flexible section between repeating units. This is illustrated as shown below where a flexible chain section such as alkyl or polyethylene can be used to connect A sections together to further improve elasticity, the structure illustrated by the below formula:




where n>=0, and the A sections are defined as follows:





wherein

    
    
        0<=x, x′, y and z<=1 and x+x′+y+z=1.
        R1 and R2 can be (CH2)nCH3, n=0-8, R3 and R4 can be (CH2)nCOOH, n=0-8, R5 and R6 can be any combination of H, COOH and COOCH3.
    
    


Most of the highly conjugated conductive polymers have rigid backbones, and the elasticity of the polymers is low. In order to accommodate volume expansion incurred during the Li interacalation and de-intercalation in the alloys, it is important that the conductive polymer binders have certain degree of elasticity. One method to increase flexibility is to synthetically introduce flexible units (n) into the polymer system as show above. Unit n is a flexible alkyl or polyethylene portion. This flexible unit (n) can be one or many of —CH2 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. One possible structure is of a random copolymer with a few percent of flexible units distributed along the fluorene main chain. The R1-R6 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 R1-R6 is also subject to change during an optimization process. One may change the number of units of the R1-R6, and look for improved cell cycling performance as indication of optimization.
Another issue is the stability and impedance of the interface between the active cathode material and electrolyte. 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 R1-R6 will play a significant role in optimizing the charge transfer impedance at the interface.
Current polymer structures that have been synthesized and tested in lithium ion battery are shown as illustrated by the below.




Once the conductive polymers have been synthesized they 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 more detailed discussion of electrode preparation is presented below. 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.
Process for Making Slurry of Conductive Polymer
Si/conductive polymer mixtures were made by dissolving 0.09 g of the conductive polymer of FIG. 1 (i.e., PFFOBA, wherein R1=R2=(CH2)7CH3, R5=COOCH3, R6=H, and x=0.5, x′=0, y=0.175 and z=0.325)) in 2.6 g of chlorobenzene. 0.18 g of Si was dispersed in the polymer solution to meet the desired Si:polymer ratios at 2:1. To ensure the thorough mixing of the Si nanoparticles into the polymer solution, 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-filled glove boxes.
Process for Making Conductive Glue of AB/PVDF
By way of comparison to the conductive polymers of this invention, illustrated in FIGS. 2 and 3, slurries of AB:PVDF (acetylene black/polyvinylidene fluoride) at 0.2:1 ratios by weight were made by dissolving 5 g of PVDF in to 95 g of NMP to make a 5% PVDF in NMP solution. Proper amounts of AB were dispersed in the PVDF solution to meet the desired AB:PVDF ratios. To ensure the thorough mixing of the AB nanoparticles into the PVDF solution, 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 glove boxes.
Process for Making Slurry of Si/AB/PVDF
0.86 g Si was mixed with 7.16 g of the conductive glue (PVDF:AB=1:0.2 by weight in 95% PVDF NMP solution). To ensure the thorough mixing of the Si nanoparticles into the glue solution, 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 about 30 min. All of the mixing processes were performed in Ar-filled glove boxes.
Process for Making the Electrode
All electrode laminates were cast onto a 20 μm 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° C. under 10−2 Torr dynamic vacuum for 24 h. The film and laminate thicknesses were measured with a Mitutoyo micrometer with an accuracy of ±1 μm. The typical thickness of film is about 20 μm. The electrodes were compressed to 35% porosity before coin cell assembly using a calender machine from International Rolling Mill equipped with a continuously adjustable gap.
Process for Fabricating Coin Cell
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 LiPF6 in EC:DEC (1:1 weight ratio) electrolyte purchased from Ferro Inc. were added to wet the electrode. A 2 cm diameter of Celgard 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. Special care was taken to align the counter electrode symmetrically above the working electrode. A stainless steel spacer and a Belleville spring were placed on top of the counter electrode. A plastic grommet was placed on top of the outer edge of the electrode assembly and crimp closed with a custom-built crimping machine manufactured by National Research Council of Canada. The entire cell fabrication procedure was done in an Ar-atmosphere glove box.
Process for Testing Coin Cell
The coin cell performance was evaluated in a thermal chamber at 30° C. with a Maccor Series 4000 Battery 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.
Chemicals
All the starting chemical materials for synthesis of the conductive polymer were purchased from Sigma-Aldrich. Battery-grade AB with an average particle size of 40 nm, a specific surface area of 60.4 m2/g, and a material density of 1.95 g/cm3 was acquired from Denka Singapore Private Ltd. PVDF KF1100 binder with a material density of 1.78 g/cm3 was supplied by Kureha, Japan Anhydrous N-methylpyrrolidone NMP with 50 ppm of water content was purchased from Aldrich Chemical Co.
As described above, 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.
Results of the various tests that were conducted are as reported in the various plots of FIGS. 2-7. FIG. 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. FIG. 3 illustrates the improved coulombic efficiency of the conductive binder/Si electrode of the invention compared with the conventional AB/PVDF approach. FIG. 4 illustrates results showing very similar voltage profiles of the conductive polymer/Si electrode to the pure Si film type of electrode. FIG. 5 plots the rate performance of the conductive polymer/Si electrode of the invention, showing good results. Evan at a 10 C rate, there is still more than half of the capacity retention. FIG. 6 illustrates cycleability 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 mAh/g fixed capacity cycling. FIG. 7 illustrates cycling results for a PFFOMB binder using an electrolyte comprising 1.2 M LiPF6 in EC/DEC (ethylene carbonate and diethylene carbonate) plus 10% FEC (fluoroethylene carbonate or fluorinated ethylene carbonate), the FEC additive serving as a stabilizer.
This invention has been described herein in considerable detail to provide those skilled in the art with information relevant to apply the novel principles and to construct and use such specialized components as are required. However, it is to be understood that the invention can be carried out by different equipment, materials and devices, and that various modifications, both as to the equipment and operating procedures, can be accomplished without departing from the scope of the invention itself.

## Claims

1. A polymeric composition with repeating units of the formula:




wherein x>=0, x′>=0, y>0, z>0, x+x′+y+z=1, R1 and R2 is (CH2)nCH3 where n=0-8, R3 and R4 is (CH2)nCOOH where n=0-8, and R5 and R6 is any combination of H, COOH and COOCH3.

2. The polymeric composition of claim 1, wherein x>0, x′=0.

3. The polymeric composition of claim 2 wherein R5 is H and R6 is COOH or COOCH3.

4. The polymeric composition of claim 1, wherein x=0, x′>0.

5. A polymer composite material comprising at least one or more micron or nano sized particles of silicon admixed with a conductive polymer binder of the formula:




wherein x>=0, x′>=0, z>0, x+x′+y+z=1, R1 and R2 is (CH2)nCH3 where n=0-8, R3 and R4 is (CH2)nCOOH where n=0-8, and R5 and R6 is any combination of H, COOH and COOCH3.

6. The polymer composite of claim 5, wherein x>0, x′=0.

7. The polymer composite of claim 6 wherein R5 is H and R6 is COOH or COOCH3.

8. The polymer composite of claim 5, wherein x=0, x′>0.

9. A method for making a silicon electrode for use in a lithium ion battery comprising the steps of:
a) forming a solution of a solvent and a conductive polymer of the formula





wherein x>=0, x′>=0, y>0, z>0, x+x′+y+z=1, R1 and R2 is (CH2)nCH3 where n=0-8, R3 and R4 is (CH2)nCOOH where n=0-8, and R5 and R6 is any combination of H, COOH and COOCH3;

b) to this solution adding micro or nano particles of silicon to form a slurry;
c) mixing the slurry to form a homogenous mixture;
d) depositing a thin film of said thus obtained mixture overtop a substrate; and,
e) drying the resulting composite to form said silicon electrode.

10. The method of claim 9, wherein the substrate is selected from the group comprising copper and aluminum.

11. The method of claim 9, wherein x>0, x′=0.

12. The method of claim 11, wherein R5 is H and R6 is COOH or COOCH3.

13. The method of claim 9, wherein x=0, x′>0.

14. A lithium ion battery having a silicon electrode incorporating a conductive polymer binder having repeating units of the formula:




wherein x>=0, x′>=0, z>0, x+x′+y+z=1, R1 and R2 is (CH2)nCH3 where n=0-8, R3 and R4 is (CH2)nCOOH where n=0-8, and R5 and R6 is any combination of H, COOH and COOCH3.

15. The battery of claim 14, wherein x>0, x′=0.

16. The battery of claim 15, wherein R5 is H and R6 is COOH or COOCH3.

17. The battery of claim 14, wherein x=0, x′>0.