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WO1992002571A1 - Polymeres solides conducteurs de cations - Google Patents

Polymeres solides conducteurs de cations Download PDF

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Publication number
WO1992002571A1
WO1992002571A1 PCT/US1991/005521 US9105521W WO9202571A1 WO 1992002571 A1 WO1992002571 A1 WO 1992002571A1 US 9105521 W US9105521 W US 9105521W WO 9202571 A1 WO9202571 A1 WO 9202571A1
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WO
WIPO (PCT)
Prior art keywords
polymer
macromolecular
solid
polymers
cation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1991/005521
Other languages
English (en)
Inventor
Subhash Narang
Sivapackia Ganapathiappan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SRI International Inc
Original Assignee
SRI International Inc
Stanford Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SRI International Inc, Stanford Research Institute filed Critical SRI International Inc
Publication of WO1992002571A1 publication Critical patent/WO1992002571A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • H01B1/122—Ionic conductors
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • 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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus

Definitions

  • the present invention relates to a broad class of cation conductive solid polymers useful in batteries, fuel cells, sensors, supercapacitors, electrochromic devices and the like.
  • electrolytes in electrochemical devices such as batteries, fuel cells, sensors, supercapacitors and eiectrochromic devices.
  • polymers which have been tested for such use are those based upon the linear-chain polyethers, poly (ethyleneoxide) and poly(propyieneoxide) with alkali metal salts.
  • Cation conductive phosphazene and siloxane polymers have also been reported which exhibit better conductivity at room temperature than do the linear-chain polyether electrolytes.
  • One class of polymers of interest are the pclyphosphazene sulfonates as reported by S.
  • Polyester conductive polymers are reported in, for example, Macromolecules 1988, 21, 96. Cation conductive siloxane comb
  • Single ion conductive polymers have an advantage over double (positive and negative) ion conductive polymers in that they can charge and discharge more completely as limitations on charging and discharging due to DC polarization is obviated.
  • the polymer electrolytes of the prior art have generally not exhibited desirable physical properties for incorporation in electrolytic devices.
  • the films may be too sticky, the polymers may be too close to being liquid, the polymers may be too
  • the present invention is directed to
  • an amorphous lomcally conductive macromolecular solid which has improved ambient temperature ionic conductivity.
  • the macromolecular solid carries a negative charge and has a positively charged ionic species associated with it.
  • the macromolecular material comprises a polymer or copolymer having a polymer backbone having a plurality of side chains extending therefrom having distal constituents having the formula:
  • X CF 2 , CFCN, CFR, or CCNR or C 6 F a R b where a is 1-4, b is 0-3 and a + b is 4 and wnere R is
  • organic or substituted organic group for example, alkyl, alkenyl, aryl, aralkyl, haloalkyl, CN, a polymer such as a polyether, a polyester, a polyamme, a polyimine, etc.
  • Y SO 3 , CO 2 or PO c where c is 2, 3 or 4, and
  • lomcally conductive macrcroiecular solid m accordance with the present invention nas a number of advantages over prior art lomcally conductive macromolecular solids.
  • the conductivity of the macromolecular solid in accordance with the present invention is generally significantly higher than tnat of the prior art macromolecular solids.
  • the macromolecular solids of the present invention have desirable physical properties in that tney can be formulated in relatively thin but still relatively highly conducting films which have
  • side cnams of the nature required by the present invention can be relatively readily added to polymers of substantially any backbone so long as such polymers have at least one active or labile hydrogen.
  • the required side chains of the present invention can be added to the monomers which are later polymerized or copolymerized to form a polymer system. Since any of a number of different polymer backbones can be
  • supercapacitor, electrochromic device, sensor or the like can, to a greater extent, choose the physical properties desired for the particular application thus providing significant added flexibility to the design of such devices.
  • a plasticizer carbe added leading to a further increase m the
  • Figure 1 illustrates a cell assembly as used for measuring conductivity
  • Figure 2 illustrates a cell and vacuum chamber as used for measuring conductivities
  • FIG. 3 illustrates, schematically, an experimental, setup as used for AC impedance
  • the present invention provides a broad class of iomcally conductive macromolecular solids.
  • macromolecular solids polymers or copolymers
  • Such macromolecular solids can have any of a great number of polymer backbones (made up of repetitive units) but are all characterized by having a plurality of side chains which have distal constituents having the formula:
  • X CF 2 , CFCN, CFR, or CCNR or C 6 F a R b where a is 1-4, b is 0-3 and a - b is 4 and where R is
  • organic or substituted organic group for example, alkyi, alkenyl, aryl, aralkyl, CN, haloalkyl, a polymer such as a polyether, a polyester, a polyamine, a polyimine, etc.
  • cation is used broadly herein to include virtually every species which can bear a positive charge and includes the elements of Groups IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB , VIA, VIB, VIIA, VIIB, AND VIII of the Periodic Table of the Elements.
  • Examples of useful polymer backbones include polyether polymers, polyester polymers, and
  • poly(ethylene) imine polymers poly(ethylene) imine polymers, polyphasphazene
  • polymers siloxane polymers, and the like.
  • the just set forth list of polymer backbones is not meant to be exhaustive buz is merely illustrative of a few of the polymers to which the side chains required by the present invention may be appended.
  • the polymers which make up the backbone of the macromolecular solid of the invention can be polymerized by the methods of the prior art.
  • the polymer backbone may also comprise a copolymer of two or more polymers with repeating units of the individual monomers.
  • the number of side chains on the macromolecular solid should be such as to provide from 0.04 to about 4 side chains per monomer unit. More preferably, the number of side chains per monomer unit falls within the range from about 0.04 to about 2.
  • any organic or substituted organic group can be present, for example, alkyl, aikenyl, aryl, aralkyl, haloalkyl, a polymer such as a polyether, a polyesrer, a
  • polyamine a polyimine, etc.
  • the cation, M can be virtually any desired catioin for a desired use, e.g., as a sensor, battery, fuel cell, supercapacitor, electrochromic device, ofr the like.
  • Batteries can be based upon, for example, having the cation be an hydrogen, a quarternary ammonium ion (NR 1 4 + where R 1 can be hydrogen, alkyl, aryl, aralkyl, aikenyl or the like), or an alkali metal cation, such as lithium, sodium, potassium, rubidium or cesium, with lithium and sodium generally being preferred.
  • the ⁇ macromolecular solid can further include an effective amount for enhancing the ionic conductivity cf the solid of a plasticizer.
  • an effective amount for enhancing the ionic conductivity cf the solid of a plasticizer Virtually any plasticizer which does not significantly lower the ionic
  • the preferred plasticizer can be represented by the formula:
  • R 2 3 C (OC 2 R 2 4 ) n CN wherein each R 2 const. tuent is independently hydrogen, alkyl, aryl, aikenyl- or aralkyl with hydrogen, methyl and ethyl being preferred and wherein n 1 to 8 inclusive.
  • a desired polymer for example, a poly (ethylene) imine polymer
  • a compound of the formula R 3 COCl in an amount sufficient to react with only a portion of the imine hydrogen to add COR 3 groups.
  • the remainder of the poly (ethylene) imine polymer backbone wili then still have imine hydrogens present.
  • the -COR containing ethyleneimme polymer can be reacted to an excess of FSO 2 CF 2 COF to provide the required side chains in accordance with the present invention, but with a fluorine attached to the terminal SO 2 group.
  • the polymer can be reacted with a metal carbonate, for example sodium carbonate, to convert it to its ionic form.
  • a metal carbonate for example sodium carbonate
  • the polymer can then be dialyzed in the presence of an excess of sodium chloride.
  • All of the CO groups in the side chains can then be reduced using, for example, BH 3 ⁇ SMe 2 followed by HCl and a base such as LiOH, NaOH or KOH .
  • a typical R 3 group would be -CH 2 O(C 2 H 4 O) m ,CH 3 but R 3 may have a multitude of other structures.
  • Cation conductive polymers with polyether side chains can be made by the following reaction scheme
  • n may be an integer or an average of integers
  • Single ion conductive ionic conducting polymers can also be prepared as set forth in
  • R CH 2 O ( C 2 H 4 O ) m CH 3
  • m is an integer or average of integers and M can suitably be Li or Na.
  • poly(ethylene) imine based electrolyte can be synthesized from monomers as per the following reaction scheme:
  • Poly (phosphazenef luorosulf cnate) home- and copolymers can be prepared as fellows: 1) [NPCl 2 ] n 2Na + [SO,CF 2 CH 2 O] 2- ⁇
  • R is C 2 H 4 OC 2 K 4 OCH 3 and x lies between 0 and 1.
  • Siloxane homo- and copolymers having the required side chains can be made as follows:
  • R (C 2 H 4 O) m CH 3 where m is an integer or average of integers;
  • the compound where X, Y and R are as previously defined can be reacted with virtually any polymer which has an available hydrogen, for example a hydrogen attached to nitrogen, sulfur or oxygen, to provide the desired side chains.
  • the group R can be virtually any alkyl, aryl, aralkyl, aikenyl, fluoroalkvl, fluoroarvl or fluoroalkenyl group or can be an oligomer such
  • Conductivities of the polymers were evaluated by AC impedance spectroscopy. Referring to the Figures, a film 6 of the dried polymer electrolyte was sandwiched between two stainless steel blocking electrodes 7,8 that each had an area of 0.7854 cm 2 .
  • the cell 10 was then perturbed with a small AC signal generated by a Solartron 1250 Frequency Response Analyzer, and the real and imaginary
  • the setup was allowed to stabilize overnight after the temperature was changed.
  • the AC impedance data were plotted in both the Nyquist and 3ode planes to identify the high frequency relaxation arising due to the polymer electrolyte.
  • the frequency of the AC signal was scanned from 65 KHz down to 10 mHz.
  • the intercept at the real axis of the high frequency relaxation was assumed to represent the resistive component of the polymer electrolyte
  • Impedance Analyzer was used to measure the polymer electrolyte resistance. This instrument has a
  • siloxane polymers in accordance with the invention and synthesized as previously described was determined and is reported in Table 4 .
  • Cation conductive solid polymers are provided in accordance with the present invention which have good physical properties and which are relatively high in conductivity whereby they are useful in the manufacture of batteries, sensors, fuel cells and the like.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Conductive Materials (AREA)
  • Secondary Cells (AREA)
  • Silicon Polymers (AREA)

Abstract

Solide macromoléculaire amorphe ioniquement conducteur présentant une conductivité ionique améliorée à température ambiante. Il comprend un solide macromoléculaire portant une charge négative et une espèce ionique chargée positivement lui est associée. La matière macromoléculaire comprend un polymère ou un copolymère présentant une pluralité de chaînes latérales dotées de constituants distaux de la formule: -X-Y- M+, dans laquelle X = CF¿2?, CFCN, CFR ou CCNR ou C6FaRb où a est compris entre 1 et 4, b est compris entre 0 et 3 et a + b valent 4, et où R répresente virtuellement n'importe quel groupe organique ou organique substitué, par exemple, alkyle, alcényle, aryle, aralkyle, haloalkyle, CN, un polymère tel qu'un polyéther, un polyester, une polyamine, une polyimine, etc., Y = SO3, CO2 ou POc où c vaut 2, 3 ou 4, et M = un cation.
PCT/US1991/005521 1990-08-03 1991-08-02 Polymeres solides conducteurs de cations Ceased WO1992002571A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US56273890A 1990-08-03 1990-08-03
US562,738 1990-08-03

Publications (1)

Publication Number Publication Date
WO1992002571A1 true WO1992002571A1 (fr) 1992-02-20

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2687671A1 (fr) * 1992-02-21 1993-08-27 Centre Nat Rech Scient Monomeres derives de sultones perhalogenees et polymeres obtenus a partir de ces monomeres.
WO1996021953A3 (fr) * 1995-01-13 1996-09-12 Stanford Res Inst Int Electrolytes de polymeres solides conducteurs monoioniques

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3187033A (en) * 1960-09-30 1965-06-01 Wacker Chemie Gmbh Sulfonated organosilicon compounds
JPS55144052A (en) * 1979-04-28 1980-11-10 Dainippon Ink & Chem Inc Production of stable organopolysiloxane emulsion polymeric liquid
US4258171A (en) * 1979-09-04 1981-03-24 The Firestone Tire & Rubber Company Polyphosphazene polymers containing substituted alkyl/cycloalkyl substituents
US4647644A (en) * 1985-05-25 1987-03-03 Degussa Aktiengesellschaft Phenylenesulfonate group-containing organopolysiloxanes, method for their preparation and use thereof
US4873293A (en) * 1986-09-30 1989-10-10 Union Carbide Chemicals And Plastics Company Inc. Partially hydrolyzed, poly(N-acyl alkylenimines) in personal care
US4960845A (en) * 1989-11-08 1990-10-02 Siltech Inc. Sulfated silicone polymers

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3187033A (en) * 1960-09-30 1965-06-01 Wacker Chemie Gmbh Sulfonated organosilicon compounds
JPS55144052A (en) * 1979-04-28 1980-11-10 Dainippon Ink & Chem Inc Production of stable organopolysiloxane emulsion polymeric liquid
US4258171A (en) * 1979-09-04 1981-03-24 The Firestone Tire & Rubber Company Polyphosphazene polymers containing substituted alkyl/cycloalkyl substituents
US4647644A (en) * 1985-05-25 1987-03-03 Degussa Aktiengesellschaft Phenylenesulfonate group-containing organopolysiloxanes, method for their preparation and use thereof
US4873293A (en) * 1986-09-30 1989-10-10 Union Carbide Chemicals And Plastics Company Inc. Partially hydrolyzed, poly(N-acyl alkylenimines) in personal care
US4960845A (en) * 1989-11-08 1990-10-02 Siltech Inc. Sulfated silicone polymers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
POLYMER COMMUNICATIONS, Vol. 30, February 1989, (ZHOU et al.), "Cation transport Electrolytes", pages 52-55. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2687671A1 (fr) * 1992-02-21 1993-08-27 Centre Nat Rech Scient Monomeres derives de sultones perhalogenees et polymeres obtenus a partir de ces monomeres.
WO1993016988A1 (fr) * 1992-02-21 1993-09-02 Centre National De La Recherche Scientifique Monomeres derives de sultones perhalogenees et polymeres obtenus a partir de ces monomeres
WO1996021953A3 (fr) * 1995-01-13 1996-09-12 Stanford Res Inst Int Electrolytes de polymeres solides conducteurs monoioniques

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