USH1546H - Solid polymer electrolyte and electrochemical cell including said electrolyte - Google Patents
Solid polymer electrolyte and electrochemical cell including said electrolyte Download PDFInfo
- Publication number
- USH1546H USH1546H US08/039,601 US3960193A USH1546H US H1546 H USH1546 H US H1546H US 3960193 A US3960193 A US 3960193A US H1546 H USH1546 H US H1546H
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- US
- United States
- Prior art keywords
- poly
- solid polymer
- polymer electrolyte
- electrolyte
- sebacate
- 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.)
- Abandoned
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Classifications
-
- 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
-
- 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
- the invention relates to solid, ionically conductive polymers and to their use as electrolytes in electrochemical cells.
- Solid polymer electrolyte (SPEs) containing dissolved metal salts have been proposed as an alternative to liquid electrolytes in rechargeable electrochemical devices.
- SPEs Solid polymer electrolyte
- the electrolyte can act as a mechanical separator between the anode and cathode, eliminating the need for an inert porous separator, as well as acting as a binder/adhesive to move and conform to electrode volume changes during cycling. Because the system would be all solid state, cells of any desired geometric shape would be possible.
- There is also a safety advantage in that if the integrity of the sealed cell package is broken, there is no liquid to leak out.
- One polymer system of interest is based on high molecular weight poly(ethylene oxide), HO--CH 2 CH 2 (O--CH 2 CH 2 ) n OH.
- An ionically solid polymer electrolyte can be prepared by dissolving PEO and an appropriate salt in a suitable volatile solvent such as acetonitrile. By solution casting, acetonitrile is removed by evaporation, leaving a free standing, solid, flexible film of good mechanical strength that contains only PEO with dissolved salt. Such films are ionic conductors. Unfortunately, at room temperature, these PEO films are highly crystalline so ionic conductivity is poor ( ⁇ 10 -7 Scm -2 ) rendering PEO as an impractical electrolyte at these temperatures.
- the general object of this invention is to provide a solid, ionically conductive polymer that can be used as an electrolyte in electrochemical cells.
- a more particular object of the invention is to improve the ionic conduction of a typical host polymer such as PEO with a dissolved lithium salt such as LiClO 4 , LiBF 4 , LiCF 3 SO 3 , or LiAsF 6 so that it can be used as an electrolyte in a solid state electrochemical cell.
- a plasticizing agent to increase the amorphous character of the polymer host and thereby enable increased ionic conductivity.
- a plasticizing agent to increase the amorphous character of the polymer host and thereby enable increased ionic conductivity.
- One such material found to act as an effective plasticizer for PEO is bis (2 ethylhexyl) sebacate, or "dioctyl" sebacate.
- the addition of dioctyl sebacate to (PEO) 20 (LiCF 3 SO 3 ) causes an immediate increase in ionic conductivity between room temperature, RT and the melting temperature of (PEO), T m .
- the increase is equal to or greater than that observed by temperature-cycled polymer without dioctyl sebacate.
- conductivities for first (temperature) cycle and subsequent cycles are indistinguishable.
- FIG. 1 shows the Log Conductivity vs. Temperature for the First Temperature Cycle for films of [PEO] 20 [LiCF 3 SO 3 ] ⁇ [Dioctyl Sebacate].
- FIG. 2 shows the Log Conductivity vs. Temperature Subsequent to the First Temperature Cycle for films of [PEO] 20 [LiCF 3 SO 3 ] ⁇ [Dioctyl Sebacate].
- Poly (ethyleneoxide), HO--CH 2 CH 2 (O--CH 2 CH 2 ) n OH (average molecular weight of 4 ⁇ 10 6 , dried at 50° C. under vacuum overnight) and lithium trifluoromethanesulfonate (LiCF 3 SO 3 , dried at 100° C. under vacuum) in molar ratios of 20:1, respectively, are dissolved in acetonitrile (distilled under a stream of dry argon) with stirring in an argon-filled glove box containing less than 10 ppm water vapor.
- a second solution is prepared with bis(2 ethylhexyl) sebacate to yield a molar ratio of 20:1:1.
- Films are cast by pouring the solutions into flat teflon dishes. After allowing the solvent to completely evaporate, free-standing films (50 to 100 ⁇ m thick) are peeled from the dishes. Films are placed between stainless steel blocking electrodes and conductivities are calculated using ac impedance measurements taken from 5 Hz to 100 kHz with an EG&G PAR Model 388 Electrochemical Impedance System.
- the ionic conductivity of films containing bis(2 ethylhexyl) sebacate is significantly higher at temperatures below T m compared to films without the additive as shown in FIG. 1 (the plasticized PEO data is for more than one film). It appears that conductivity is enhanced slightly at temperatures above T m as well. This renders the film more practical for use in an electrochemical cell since batteries are ordinarily used at room temperature. Further improvements by the addition of other salts or plasticizers and refinements in the molar ratios used may produce films with even higher conductivities.
- FIG. 2 shows conductivity vs temperature for temperature cycles subsequent to the first cycle.
- Plasticized films maintain comparable or better conductivity than un-plasticized films.
- conductivity for first (temperature) cycle and subsequent cycles are indistinguishable.
- Li + associates with oxygen molecules on PEO, it is possible that bis(2 ethylhexyl) sebacate performs a dual role, increasing the amorphous nature of PEO and also complexing/coordinating lithium ions with the oxygen molecules on itself. Other substances of similar configurations might also be expected to be useful in augmenting ionic conductivity.
- poly(ethylene oxide) as the polymer host, one may use at least one of the following, poly(propylene oxide) and mixtures of poly(ethylene oxide) and poly(propylene oxide).
- plasticizing agents such as LiN(CF 3 SO 2 ) 2 , propylene carbonate-ethylene carbonate mixtures, triethylene glycol dimetharylate, and esters of phthalic, adipic, and phosphoric acids.
- the anode of an electrochemical cell including the solid polymer electrolyte and plasticizer may be either lithium, a lithium alloy, or a lithium intercalate such as LiC 6 , graphite, or petroleum coke.
- the cathode may be a metal oxide such as Ag 2 CrO 4 , CuO, Bi 2 O 3 , Bi 2 Pb 2 O 5 , CrO x , MnO 2 , Li x MnO y , MoO 3 , MoO 3 , LiNiO 2 , V 2 O 5 , V 6 O 13 , LiCoO 2 or sulfide such as CuS, FeS x , TiS 2 , MoS 2 , Cr x V 1-x S 2 , Ni 3 S 2 , or fluoride such as CuF 2 (CF) n or chloride such as CuCl 2 , AgCl or acetylene black carbon, or lithium intercalating compound, or electrically conductive polymer such as polyactylene, poly (alky
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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
Abstract
A solid polymer electrolyte is provided including a solid solution of a lium salt such as LiCF3 SO3 in a polymer host such as poly(ethylene oxide). The electrolyte also includes a small amount of a plasticizing agent such as bis(2 ethylhexyl) sebacate. The electrolyte can be used to make a solid state electrochemical cell.
Description
The invention described herein may be manufactured, used, and licensed by or for the Government for governmental purposes without the payment to me of any royalties thereon.
The invention relates to solid, ionically conductive polymers and to their use as electrolytes in electrochemical cells.
Solid polymer electrolyte (SPEs) containing dissolved metal salts have been proposed as an alternative to liquid electrolytes in rechargeable electrochemical devices. There are many advantages to using a solid electrolyte, such as the capability for high speed production of thin cells constructed in a bipolar arrangement. Further, the electrolyte can act as a mechanical separator between the anode and cathode, eliminating the need for an inert porous separator, as well as acting as a binder/adhesive to move and conform to electrode volume changes during cycling. Because the system would be all solid state, cells of any desired geometric shape would be possible. There is also a safety advantage in that if the integrity of the sealed cell package is broken, there is no liquid to leak out.
One polymer system of interest is based on high molecular weight poly(ethylene oxide), HO--CH2 CH2 (O--CH2 CH2)n OH. An ionically solid polymer electrolyte can be prepared by dissolving PEO and an appropriate salt in a suitable volatile solvent such as acetonitrile. By solution casting, acetonitrile is removed by evaporation, leaving a free standing, solid, flexible film of good mechanical strength that contains only PEO with dissolved salt. Such films are ionic conductors. Unfortunately, at room temperature, these PEO films are highly crystalline so ionic conductivity is poor (≈10-7 Scm-2) rendering PEO as an impractical electrolyte at these temperatures.
The general object of this invention is to provide a solid, ionically conductive polymer that can be used as an electrolyte in electrochemical cells. A more particular object of the invention is to improve the ionic conduction of a typical host polymer such as PEO with a dissolved lithium salt such as LiClO4, LiBF4, LiCF3 SO3, or LiAsF6 so that it can be used as an electrolyte in a solid state electrochemical cell.
It has now been found that the aforementioned objects can be attained by the addition of a plasticizing agent to increase the amorphous character of the polymer host and thereby enable increased ionic conductivity. One such material found to act as an effective plasticizer for PEO is bis (2 ethylhexyl) sebacate, or "dioctyl" sebacate. The addition of dioctyl sebacate to (PEO)20 (LiCF3 SO3), causes an immediate increase in ionic conductivity between room temperature, RT and the melting temperature of (PEO), Tm. The increase is equal to or greater than that observed by temperature-cycled polymer without dioctyl sebacate. In polymer containing dioctyl sebacate, conductivities for first (temperature) cycle and subsequent cycles are indistinguishable.
FIG. 1 shows the Log Conductivity vs. Temperature for the First Temperature Cycle for films of [PEO]20 [LiCF3 SO3 ]±[Dioctyl Sebacate].
FIG. 2 shows the Log Conductivity vs. Temperature Subsequent to the First Temperature Cycle for films of [PEO]20 [LiCF3 SO3 ]±[Dioctyl Sebacate].
Poly (ethyleneoxide), HO--CH2 CH2 (O--CH2 CH2)n OH (average molecular weight of 4×106, dried at 50° C. under vacuum overnight) and lithium trifluoromethanesulfonate (LiCF3 SO3, dried at 100° C. under vacuum) in molar ratios of 20:1, respectively, are dissolved in acetonitrile (distilled under a stream of dry argon) with stirring in an argon-filled glove box containing less than 10 ppm water vapor. A second solution is prepared with bis(2 ethylhexyl) sebacate to yield a molar ratio of 20:1:1. Films are cast by pouring the solutions into flat teflon dishes. After allowing the solvent to completely evaporate, free-standing films (50 to 100 μm thick) are peeled from the dishes. Films are placed between stainless steel blocking electrodes and conductivities are calculated using ac impedance measurements taken from 5 Hz to 100 kHz with an EG&G PAR Model 388 Electrochemical Impedance System.
The ionic conductivity of films containing bis(2 ethylhexyl) sebacate is significantly higher at temperatures below Tm compared to films without the additive as shown in FIG. 1 (the plasticized PEO data is for more than one film). It appears that conductivity is enhanced slightly at temperatures above Tm as well. This renders the film more practical for use in an electrochemical cell since batteries are ordinarily used at room temperature. Further improvements by the addition of other salts or plasticizers and refinements in the molar ratios used may produce films with even higher conductivities.
FIG. 2 shows conductivity vs temperature for temperature cycles subsequent to the first cycle. Plasticized films maintain comparable or better conductivity than un-plasticized films. In films containing dioctyl sebacate, conductivity for first (temperature) cycle and subsequent cycles are indistinguishable.
Since Li+ associates with oxygen molecules on PEO, it is possible that bis(2 ethylhexyl) sebacate performs a dual role, increasing the amorphous nature of PEO and also complexing/coordinating lithium ions with the oxygen molecules on itself. Other substances of similar configurations might also be expected to be useful in augmenting ionic conductivity.
In lieu of poly(ethylene oxide) as the polymer host, one may use at least one of the following, poly(propylene oxide) and mixtures of poly(ethylene oxide) and poly(propylene oxide).
Similarly, other plasticizing agents may be used in the invention such as LiN(CF3 SO2)2, propylene carbonate-ethylene carbonate mixtures, triethylene glycol dimetharylate, and esters of phthalic, adipic, and phosphoric acids.
Though the preferred embodiment shows a molar ratio of PEO:salt:plasticizer of 20:1:1, alternate ratios may be used to optimize performance characteristics.
The anode of an electrochemical cell including the solid polymer electrolyte and plasticizer may be either lithium, a lithium alloy, or a lithium intercalate such as LiC6, graphite, or petroleum coke. The cathode may be a metal oxide such as Ag2 CrO4, CuO, Bi2 O3, Bi2 Pb2 O5, CrOx, MnO2, Lix MnOy, MoO3, MoO3, LiNiO2, V2 O5, V6 O13, LiCoO2 or sulfide such as CuS, FeSx, TiS2, MoS2, Crx V1-x S2, Ni3 S2, or fluoride such as CuF2 (CF)n or chloride such as CuCl2, AgCl or acetylene black carbon, or lithium intercalating compound, or electrically conductive polymer such as polyactylene, poly (alkyl-thiophene), polyaniline, phenylene, phenylene sulfide, or mixtures thereof; including a solid polymer electrolyte. The electrochemical cell containing such an anode, solid polymer electrolyte containing plasticizer, and cathode may be primary (nonrechargeable) or secondary (rechargeable).
I wish it to be understood that I do not desire to be limited to the exact details of construction shown and described for obvious modification will occur to a person skilled in the art.
Claims (9)
1. A solid polymer electrolyte including a solution of at least one lithium salt in at least one polymer host, and wherein said electrolyte includes a plasticizing agent.
2. A solid polymer electrolyte according to claim 1 wherein said polymer host is at least one polymer selected from the group consisting of poly(ethylene oxide) (PEO), polyacetylene, poly(alkyl-thiophene), polyaniline, phenylene, and phenylene sulfide, wherein said lithium salt is at least one salt selected from the group consisting of LiClO4, LiBF4, LiCF3 SO3, and LiAs F6 and wherein said plasticizing agent is selected from the group consisting of bis(2 ethylhexyl) sebacate, mixtures of propylene carbonate and ethylene carbonate, triethylene glycol dimethacrylate, esters of phthalic acid, esters of adipic acid, and esters of phosphoric acid.
3. A solid polymer electrolyte according to claim 2 wherein said polymer host is poly(ethylene oxide), said lithium salt is LiCF3 SO3, and said plasticizing agent is bis(2 ethylhexyl ) sebacate.
4. A solid polymer electrolyte according to claim 3 wherein the ratio by weight of poly(ethylene oxide):LiCF3 SO3 : bis(2 ethylhexyl sebacate) is 20:1:1.
5. An electrochemical cell including an anode selected from the group consisting of lithium metal, lithium alloy, LiC6, graphite, and petroleum coke, a cathode selected from the group consisting of Ag2 CrO4, CuO, Bi2 O3, Bi2 Pb2 O5, CrOx, MnO2, Lix MnOy, MoO3, LiNiO2, V2 O5, V6 O13, LiCoO2, CuS, FeS2, TiS2, MoS2, Crx V1-x, S2, Ni3 S2, CuF2, (CF)n, CuCl2, and AgCl and a solid polymer electrolyte including a solid solution of at least one lithium salt in at least one polymer host, and said electrolyte including a plasticizing agent.
6. An electrochemical cell according to claim 5 wherein the solid polymer electrolyte includes a solid solution of LiCF3 CO3 in poly(ethylene oxide); the solid polymer electrolyte also including bis(2 ethylhexyl) sebacate.
7. A rechargeable electrochemical cell according to claim 6 wherein the polymer is poly(ethylene oxides), wherein the salt is LiCF3 SO3, and wherein the plasticizing agent is bis(2 ethylhexyl) sebacate.
8. An electrochemical cell according to claim 6 wherein the cell is a rechargeable cell.
9. An electrochemical cell according to claim 7 wherein the cell is a primary cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/039,601 USH1546H (en) | 1993-03-16 | 1993-03-16 | Solid polymer electrolyte and electrochemical cell including said electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/039,601 USH1546H (en) | 1993-03-16 | 1993-03-16 | Solid polymer electrolyte and electrochemical cell including said electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USH1546H true USH1546H (en) | 1996-06-04 |
Family
ID=21906350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/039,601 Abandoned USH1546H (en) | 1993-03-16 | 1993-03-16 | Solid polymer electrolyte and electrochemical cell including said electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USH1546H (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030138702A1 (en) * | 2001-12-10 | 2003-07-24 | Gerald Rex E. | High cation transport polymer electrolyte |
| US9590269B2 (en) | 2013-12-31 | 2017-03-07 | Industrial Technology Research Institute | Polyelectrolyte and energy storage device |
| CN114006027A (en) * | 2020-07-27 | 2022-02-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | Molybdenum disulfide-based composite solid electrolyte, preparation method and application thereof |
| US20240290517A1 (en) * | 2022-01-24 | 2024-08-29 | Lanzhou Institute Of Chemical Physics, Chinese Academy Of Sciences | Oil-soluble conductive additive and preparation method therefor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5143805A (en) * | 1986-03-24 | 1992-09-01 | W. R. Grace & Co.-Conn: | Cathodic electrode |
| US5183715A (en) * | 1987-02-18 | 1993-02-02 | Gould Electronics Limited | Solid state cell electrolyte |
-
1993
- 1993-03-16 US US08/039,601 patent/USH1546H/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5143805A (en) * | 1986-03-24 | 1992-09-01 | W. R. Grace & Co.-Conn: | Cathodic electrode |
| US5183715A (en) * | 1987-02-18 | 1993-02-02 | Gould Electronics Limited | Solid state cell electrolyte |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030138702A1 (en) * | 2001-12-10 | 2003-07-24 | Gerald Rex E. | High cation transport polymer electrolyte |
| US7226549B2 (en) * | 2001-12-10 | 2007-06-05 | Uchicago Argonne, Llc | High cation transport polymer electrolyte |
| US9590269B2 (en) | 2013-12-31 | 2017-03-07 | Industrial Technology Research Institute | Polyelectrolyte and energy storage device |
| CN114006027A (en) * | 2020-07-27 | 2022-02-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | Molybdenum disulfide-based composite solid electrolyte, preparation method and application thereof |
| CN114006027B (en) * | 2020-07-27 | 2023-08-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Molybdenum disulfide-based composite solid electrolyte, and preparation method and application thereof |
| US20240290517A1 (en) * | 2022-01-24 | 2024-08-29 | Lanzhou Institute Of Chemical Physics, Chinese Academy Of Sciences | Oil-soluble conductive additive and preparation method therefor |
| US12406778B2 (en) * | 2022-01-24 | 2025-09-02 | Lanzhou Institute Of Chemical Physics, Chinese Academy Of Sciences | Oil-soluble conductive additive and preparation method therefor |
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