USH1054H - Electrochemical cell that delivers high power pulses - Google Patents

Electrochemical cell that delivers high power pulses Download PDF

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Publication number
USH1054H
USH1054H US07/715,265 US71526591A USH1054H US H1054 H USH1054 H US H1054H US 71526591 A US71526591 A US 71526591A US H1054 H USH1054 H US H1054H
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US
United States
Prior art keywords
electrolyte
pmt
lialcl
electrochemical cell
alcl
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Abandoned
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US07/715,265
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English (en)
Inventor
Charles W. Walker, Jr.
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United States Department of the Army
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United States Department of the Army
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Priority to US07/715,265 priority Critical patent/USH1054H/en
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Publication of USH1054H publication Critical patent/USH1054H/en
Priority to CA002069181A priority patent/CA2069181C/fr
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This invention relates in general to an electrochemical cell that delivers high power pulses and in particular to such a cell that includes poly 3-methylthiophene, PMT as the cathode, a member of the group consisting of Li(SO 2 ) 3 AlCl 4 , 1.0M LiAlCl 4 --SOCl 2 , and 1.0 M LiAlCl 4 --SO 2 Cl 2 as the electrolyte, and lithium as the anode.
  • the general object of this invention is to provide an electrochemical cell capable of delivering high power pulses.
  • a more specific object of the invention is to provide a lithium electrochemical cell able to deliver high power pulses over seconds or minutes with volumetric power density exceeding porous carbon cathode technology.
  • an electrochemical cell including PMT as the cathode, a member of the group consisting of Li(SO 2 ) 3 AlCl 4 , 1.0 M LiAlCl 4 --SOCl 2 and 1.0 M LiAlCl 4 --SO 2 Cl 2 as the electrolyte, and lithium as the anode.
  • Thin films of PMT can be easily polymerized electrochemically, controlling film thickness by the number of coulombs of charge passed.
  • PMT When reduced (undoped), PMT is electrically insulating, but in the doped state, has an electrical conductivity in the range of 10-2000 S cm -1 depending on the method of preparation and dopant anion.
  • Controlling polymerization electrochemically allows fabrication of conductive films that are much thinner than cathodes prepared, for example, with Teflon-bonded porous carbon.
  • the polymer films can be pulse discharged in Li(SO 2 ) 3 AlCl 4 ,1 M LiAlCl 4 --SOCl 2 and 1.0 M LiAlCl 4 --SO 2 Cl 2 electrolytes to yield very high volumetric power densities. Power levels per cm 3 of polymer cathode are substantially higher than for Teflon bonded porous carbon cathodes.
  • thin, electrically conducting PMT films are formed electrochemically and used as cathodes in electrochemical cells.
  • the pulse power capabilities of 1.4 ⁇ m thick PMT films discharged in Li(SO 2 ) 3 AlCl 4 , 1.0 M LiAlCl 4 --SO 2 Cl 2 and 1.0 M LiAICl 4 --SOCl 2 are determined.
  • a volumetric power density (for PMT) of 600 W cm -3 is sustained for 30 seconds at an operating potential of about 3.0 V in both thionyl chloride (SOCl 2 ) and sulfuryl chloride (SO 2 Cl 2 ).
  • a power density of 429 W cm -3 is sustained for 2 minutes (operating at approximately 3.0 V) when PMT is discharged in SOCl 2 .
  • Power densities are less in the sulfur dioxide based electrolyte, but the PMT cathode is able to be discharged and recharged for many cycles. Multiple 4 second pulses in the SO 2 electrolyte averaging about 300 W cm are reproducible over many cycles.
  • polymer cathode is obtainable that is electrically conductive and able to be tailored to any desired thickness by the amount of charge passed during electropolymerization. Thicknesses on the order of one micron are easily fabricated, whereas Teflon-bonded porous carbon cathodes are necessarily much thicker.
  • Power densities of 600 W cm -3 can be sustained for at least 30 seconds at a 3.0 V operating potential.
  • Polymerization of PMT can be carried out in a 125 ml European flask (Ace Glass) using a 1 cm 2 platinum flag counter electrode, a SSCE reference electrode, and a platinum or glassy carbon rod working electrode.
  • Glassy carbon and platinum rods (0.071 cm 2 cross section) are polished to a mirror finish with a 0.1 micron alumina/water paste.
  • the rod is sheathed in heat shrinkable Teflon so as to expose only the cross sectional area at the end of the rod.
  • the cell is flooded with electrolyte containing 0.1 M 3-methylthiophene monomer (Sigma Chemical, 99+%) and 0.1 M tetrabutylammonium tetrafluoroborate (Alpha), with redistilled acetonitrile (Fisher) as the solvent.
  • electrolyte containing 0.1 M 3-methylthiophene monomer (Sigma Chemical, 99+%) and 0.1 M tetrabutylammonium tetrafluoroborate (Alpha), with redistilled acetonitrile (Fisher) as the solvent.
  • Ultra high purity dry argon is bubbled through the electrolyte to remove oxygen.
  • Adherent films 1.4 ⁇ m thick (measured by SEM), are fabricated at 10 mA cm -2 by a pulse deposition process, where 0.25 C cm -2 is passed in five cycles with five minute rest periods (at open circuit) between cycles.
  • the PMT-coated rod is then rinsed in acetonitrile and dried under vacuum at 50° C.
  • a maximum of 4.52 ⁇ 10 -5 g of 3-methylthiophene is deposited on the substrate. Based on the cross-sectional area and thickness, the volume of the film is 9.95 ⁇ 10 -6 cm 3 .
  • Li(SO 2 ) 3 AlCl 4 electrolyte is prepared with anhydrous LiAlCl 4 (Anderson Physics) and excess dry liquid SO 2 (Matheson) by combining them in an evacuated Teflon cell (able to withstand pressure). After dissolution of the salt, excess SO 2 is slowly bled off through a bubbler containing halocarbon oil. The resultant electrolyte is between 3 and 3.5 SO 2 molecules per LiAlCl 4 molecule as measured by weight. Anhydrous LiCl is added to scavenge any excess AlCl 3 and ensure a neutral electrolyte. Electrolytes containing sulfuryl chloride and thionyl chloride are prepared by dissolving LiAlCl 4 (Anderson Physics) to form a 1.0 molar solution, then adding anhydrous LiCl to ensure solution neutrality.
  • PMT Upon polymeriztion in the acetonitrile-based electrolyte, PMT is doped with BF 4 - anions. Constant current discharge capacity in Li(SO 2 ) 3 AlCl 4 electrolyte is improved when BF 4 - dopant ions are replaced with AlCI 4 - from the electrolyte. Therefore, all experiments with Li(SO 2 ) 3 AlCl 4 electrolyte are performed with AlCl 4 - -doped PMT.
  • the usual method of treatment is to undope BF 4 - from the polymer in LiAlCl 4 -3SO 2 electrolyte by holding the potential at 3.0 V (vs lithium) and then doping AlCl 4 - by charging at a constant potential of 3.8 V.
  • a PAR Model 173 potentiostat/galvanostat with a model 276 plug-in interface is used in conjunction with a Hewlett Packard HP-86 computer.
  • the experimental cell for the pulse experiments is a 125 ml European flask flooded with 20 ml of Li(SO 2 ) 3 AlCl 4 electrolyte, containing a large lithium counter electrode and lithium reference.
  • FIG. 1 shows voltage and power density as a function of discharge time at 10 mA cm -2 constant current, for a 1.4 ⁇ m thick PMT cathode and lithium anode in either 1.0 M LiAlCl 4 --SOCl 2 , 1.0 M LiAlCl 4 --SO 2 Cl 2 , or Li(SO 2 ) 3 AlCl 4 electrolyte.
  • FIG. 2 shows voltage and power density as a function of discharge time at 20 mA cm -2 constant current, for a 1.4 ⁇ m thick PMT cathode and lithium anode in either 1.0 M LiAlCl 4 --SOCl 2 , 1.0 M LiAlCl 4 --SO 2 Cl 2 , or Li(SO 2 ) 3 AlCl 4 electrolyte.
  • FIG. 3 shows voltage and power density as a function of discharge time at 30 mA cm -2 constant current, for a 1.4 ⁇ m thick PMT cathode and lithium anode in either 1.0 M LiAlCl 4 --SOCl 2 , 1.0 M LiAlCl 4 --SO 2 Cl 2 , or Li(SO 2 ) 3 AlCl 4 electrolyte.
  • FIG. 4 shows power and current density for up to 5 s following a potential step from open circuit to 2.6 V.
  • Li/Li(SO 2 ) 3 AlCl 4 cell with 1.4 ⁇ m thick PMT (circle) and 1090 ⁇ m thick PTFE-bonded 75% Sawinigan-25% Ketjen black cathode (square).
  • FIG. 5 shows final potential of Li/Li(SO 2 ) 3 AlCl 4 /1.4 ⁇ m PMT cell after each 4 second, 15 mA cm -2 pulse with 1 s open circuit rest periods. Recharge is at 0.2 mA cm -2 to a 3.8 V cutoff. First (square) and 21st (circle) pulse sets are shown.
  • FIG. 6 shows final potential of Li/Li(SO 2 ) 3 AlCl 4 /1.4 ⁇ m PMT cell after each 4 second, 25 mA cm -2 pulse with 1 s open circuit rest periods. Recharge is at 0.2 mA cm -2 to a 3.8 V cutoff. Second (square) and 35th (circle) pulse sets are shown.
  • Constant current discharge of PMT is carried out at 10, 20 and 30 mA cm -2 .
  • Cell potential and volumetric power density are shown in FIGS. 1-3.
  • Lowest operating potential and shortest discharge times are observed in the sulfur dioxide based electrolyte.
  • the sulfuryl chloride electrolyte initially provides the highest operating potential, the thionyl chloride based electrolyte has the longest cell capacity at all current densities.
  • PMT can deliver about 600 W cm -3 at a potential of 3.0 V in both sulfuryl chloride and thionyl chloride for at least 0.5 minutes.
  • PMT can be discharged for 1.25 minutes at power densities above 400 W cm -3 .
  • PMT in thionyl chloride can be discharged for nearly 2 minutes at a 3.0 V operating potential and 429 W cm -3 power density.
  • discharge in sulfur dioxide is poor.
  • PMT is able to be cycled (discharged and charged) in the SO 2 -based electrolyte.
  • pulse power (potential step to 2.6 V) is shown for up to five seconds, whereafter 1.4 ⁇ m thick PMT delivers about 0.07 W cm -2 (26 mA cm -2 ; 489 W cm -3 ).
  • PMT potential step to 2.6 V
  • the area and volume of this electrode are 0.5 cm 2 (counting both sides of a 0.25 cm 2 cathode) and 0.027 cm 3 respectively.
  • the polymer film provides a vast improvement in power density compared to the established Teflon-bonded porous carbon technology.
  • the thick porous carbon electrode sustains a high current density (135 mA cm -2 ) after 5 s; however, PMT delivers more power per cm 2 for nearly one second.
  • the power densities for PMT and porous carbon are 489 W cm -3 and 6.5 W cm -3 respectively shown in Table 1.
  • Table 1 shows a comparison of current density and power density for 1.4 ⁇ m thick PMT and 1090 ⁇ m thick PTFE-bonded porous carbon (75% Shawinigan, 25% Ketjen black) cathodes.
  • the Li/Li(SO 2 ) 3 AlCl 4 /cathode cell stepped from OCV to 2.6 V.
  • PMT is superior to thicker porous carbon electrodes, and can be more easily fabricated as a bipolar stack of very thin electrodes.
  • the superior pulse power of PMT (compared to porous carbons) is not a result of polymer surface area (4.13 m 2 g- 1 , measured by a one point BET surface area analysis) since carbon blacks have much greater surface areas (60-1500 m 2 g -1 ).
  • PMT is also evaluated for intermittent constant current pulse power in Li (SO 2 ) 3 AlCl 4 electrolyte.
  • a constant current load is applied for four seconds, and cell potential measured at the end of this period. Following a one second rest at open circuit, the cell is pulsed again, repeating this procedure until cell potential falls below 2.0 V. Then the cell is recharged at 0.2 mA cm -2 to a 3.8 V cutoff, after which the next cycle is begun.
  • the potential at the end of each four second pulse is shown in FIGS. 5 and 6.
  • PMT is pulse discharged at 15 mA cm -2 . In the first set of pulse discharges, eight pulses are obtained. After 20 cycles, the 21st set also provides eight pulses.
  • FIG. 6 shows data at a 25 mA cm -2 rate. Here, four or five pulses are obtained for 35 cycles. The first three pulses are very reproducible, with final potentials between 2.9 and 2.6 V and power densities of 518 to 464 W cm -3 respectively.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
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US07/715,265 1991-06-14 1991-06-14 Electrochemical cell that delivers high power pulses Abandoned USH1054H (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US07/715,265 USH1054H (en) 1991-06-14 1991-06-14 Electrochemical cell that delivers high power pulses
CA002069181A CA2069181C (fr) 1991-06-14 1992-05-21 Cellule electrochimique produisant des impulsions de haute puissance

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150207172A1 (en) * 2013-02-07 2015-07-23 Alevo Research Ag Process for producing electrolyte for electrochemical battery cell

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7624630B2 (ja) * 2019-02-28 2025-01-31 パナソニックＩｐマネジメント株式会社 電解質材料およびそれを用いた電池

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4472488A (en) 1983-11-30 1984-09-18 Allied Corporation Polymeric electrode coated with reaction product of cyclic compound
US4543306A (en) 1982-06-01 1985-09-24 Thomson-Csf Electrochemical device which can be used for energy storage
US4547441A (en) 1984-12-03 1985-10-15 Saft Electrochemical cell with negative active material based on an alkali or alkaline earth metal
US4556617A (en) 1984-06-26 1985-12-03 Raychem Corporation Anhydrous primary battery
US4772517A (en) 1985-02-26 1988-09-20 Basf Aktiengesellschaft Composite electrode
US4803138A (en) 1987-03-13 1989-02-07 Showa Denko K.K. & Hitachi, Ltd. Nonaqueous secondary battery
US4816359A (en) 1986-03-06 1989-03-28 Varta Batterie Aktiengesellschaft Electrochemical secondary element with at least one polymer electrode
US4957833A (en) 1988-12-23 1990-09-18 Bridgestone Corporation Non-aqueous liquid electrolyte cell
US4987042A (en) 1988-04-22 1991-01-22 Bayer Aktiengesellschaft Polythiophenes, process for their preparation and their use

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4543306A (en) 1982-06-01 1985-09-24 Thomson-Csf Electrochemical device which can be used for energy storage
US4472488A (en) 1983-11-30 1984-09-18 Allied Corporation Polymeric electrode coated with reaction product of cyclic compound
US4556617A (en) 1984-06-26 1985-12-03 Raychem Corporation Anhydrous primary battery
US4547441A (en) 1984-12-03 1985-10-15 Saft Electrochemical cell with negative active material based on an alkali or alkaline earth metal
US4772517A (en) 1985-02-26 1988-09-20 Basf Aktiengesellschaft Composite electrode
US4816359A (en) 1986-03-06 1989-03-28 Varta Batterie Aktiengesellschaft Electrochemical secondary element with at least one polymer electrode
US4803138A (en) 1987-03-13 1989-02-07 Showa Denko K.K. & Hitachi, Ltd. Nonaqueous secondary battery
US4987042A (en) 1988-04-22 1991-01-22 Bayer Aktiengesellschaft Polythiophenes, process for their preparation and their use
US4957833A (en) 1988-12-23 1990-09-18 Bridgestone Corporation Non-aqueous liquid electrolyte cell

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150207172A1 (en) * 2013-02-07 2015-07-23 Alevo Research Ag Process for producing electrolyte for electrochemical battery cell
US9515349B2 (en) * 2013-02-07 2016-12-06 Alevo International S.A. Process for producing electrolyte for electrochemical battery cell

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CA2069181A1 (fr) 1992-12-15
CA2069181C (fr) 1997-04-01

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