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1,9,10-Substituted Phenothiazine Derivatives with Strained Radical Cations and Use Thereof

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1,9,10-Substituted Phenothiazine Derivatives with Strained Radical Cations and Use Thereof University of Kentucky UKnowledge Chemistry Faculty Patents Chemistry 12-1-2020 1,9,10-Substituted Phenothiazine Derivatives with Strained Radical Cations and Use Thereof Susan A. Odom University of Kentucky, [email protected] Chad Risko University of Kentucky, [email protected] Matthew D. Casselman University of Kentucky Corrine F. Elliott University of Kentucky, [email protected] Nuwan Harsha Attanayake University of Kentucky, [email protected] See next page for additional authors Follow this and additional works at: https://uknowledge.uky.edu/chemistry_patents Part of the Chemistry Commons Right click to open a feedback form in a new tab to let us know how this document benefits ou.y Recommended Citation Odom, Susan A.; Risko, Chad; Casselman, Matthew D.; Elliott, Corrine F.; Attanayake, Nuwan Harsha; and Modekrutti, Subrahmanyam, "1,9,10-Substituted Phenothiazine Derivatives with Strained Radical Cations and Use Thereof" (2020). Chemistry Faculty Patents. 42. https://uknowledge.uky.edu/chemistry_patents/42 This Patent is brought to you for free and open access by the Chemistry at UKnowledge. It has been accepted for inclusion in Chemistry Faculty Patents by an authorized administrator of UKnowledge. For more information, please contact [email protected]. Authors Susan A. Odom, Chad Risko, Matthew D. Casselman, Corrine F. Elliott, Nuwan Harsha Attanayake, and Subrahmanyam Modekrutti This patent is available at UKnowledge: https://uknowledge.uky.edu/chemistry_patents/42 I 1111111111111111 1111111111 lllll lllll lllll 111111111111111 111111111111111111 US010854911B2 c12) United States Patent (IO) Patent No.: US 10,854,911 B2 Odom et al. (45) Date of Patent: Dec. 1, 2020 (54) 1,9,10-SUBSTITUTED PHENOTHIAZINE (58) Field of Classification Search DERIVATIVES WITH STRAINED RADICAL None CATIONS AND USE THEREOF See application file for complete search history. (56) References Cited (71) Applicant: University of Kentucky Research Foundation, Lexington, KY (US) U.S. PATENT DOCUMENTS (72) Inventors: Susan A. Odom, Lexington, KY (US); 2008/0296169 Al* 12/2008 Davidson .................. C25B 1/04 Chad Risko, Lexington, KY (US); 205/337 Matthew D. Casselman, Lexington, 2017/0062842 Al* 3/2017 Huang C07D 279/22 2017/0244132 Al* 8/2017 Wagner. H0lM 10/0525 KY (US); Corrine F. Elliott, Lexington, KY (US); N. Harsha FOREIGN PATENT DOCUMENTS Attanayake, Lexington, KY (US); Subrahmanyam Modekrutti, WO WO-2016011393 Al * 1/2016 ........ H0lM 10/0525 Lexington, KY (US) OTHER PUBLICATIONS (73) Assignee: University of Kentucky Research Foundation, Lexington, KY (US) Casselman, et al., Beyond the Hammett Effect: Using Strain to Alter the Landscape of Electrochemical Potentials; ChemPhysChem 2017, ( * ) Notice: Subject to any disclaimer, the term ofthis 18, 2142-2146. patent is extended or adjusted under 35 (Continued) U.S.C. 154(b) by O days. Primary Examiner - Amanda C. Walke (21) Appl. No.: 15/654,464 (74) Attorney, Agent, or Firm - Stites & Harbison PLLC; Mandy Wilson Decker; Summer Elizabeth Young (22) Filed: Jul. 19, 2017 (57) ABSTRACT (65) Prior Publication Data Compounds for use in a rechargeable battery are provided, US 2018/0026297 Al Jan. 25, 2018 including a compound according to the formula: Related U.S. Application Data (60) Provisional application No. 62/364,060, filed on Jul. 19, 2016. (51) Int. Cl. H0lM 101056 (2010.01) C07D 279122 (2006.01) wherein R 1 and R9 are independently selected from the (Continued) group consisting of H, alkyl, aryl, perfluoroaryl, perfluoro­ (52) U.S. Cl. alkyl, alkylaryl, alkoxyaryl, alkylcarboxyl, aryl carbonyl, CPC ........ H0lM 101056 (2013.01); C07D 279120 haloalkyl, perfluoroalkyl, glycols, haloaryl, a negative elec­ (2013.01); C07D 279122 (2013.01); trolyte, and a polymer, so long as when R 1 is H, ~ is not H; (Continued) (Continued) R~Me MPT R1 =CH3 3,7.. QMeEPT R ~Et 1 Et EPT R ~· CF:3 3~7 "BCF3EPT iPr iPr iPrPT Ph tBu tSuPT Ph PhPT US 10,854,911 B2 Page 2 and R10 is selected from the group consisting of methyl, (52) U.S. Cl. alkyl, aryl, alkylaryl, alkoxyaryl, alkylcarboxyl, aryl carbo­ CPC ........... H0lM 41131 (2013.01); H0lM 41133 nyl, haloalkyl, perfluoroalkyl, perfluoroaryl, glycols, (2013.01); H0lM 8/18 (2013.01); H0lM haloaryl, an oligomer, and a polymer. 8/188 (2013.01); H0lM 1010525 (2013.01); H0lM 1010567 (2013.01); H0JM 4/587 21 Claims, 15 Drawing Sheets (2013.01); H0JM 2004/027 (2013.01); H0JM 2004/028 (2013.01); Y02E 60/50 (2013.01) (51) Int. Cl. (56) References Cited C07D 279120 (2006.01) H0lM 1010525 (2010.01) OTHER PUBLICATIONS H0lM 41133 (2010.01) H0lM 41131 (2010.01) Casselman, et al., Supporting Information Beyond the Hammett H0lM 8/18 (2006.01) Effect: Using Strain to Alter the Landscape of Electrochemical H0lM 1010567 (2010.01) Potentials, pp. 1-17, (2017). H0JM 4/02 (2006.01) H0JM 4/587 (2010.01) * cited by examiner U.S. Patent Dec. 1, 2020 Sheet 1 of 15 US 10,854,911 B2 R.:::::Me MPT R':z:CH3 3,7.;DMeEPT R :::::Et Et E.PT R' :z: CF:1 3,7-SCF#;PT iPr iPr iPrPT Ph mu tBuPT Ph PhPT Figure 1 radkal Ii cation Reaction Coordinate Figure 2 J i~::::~/;:::'~,-.:;=,::.... --------==,·····, ••••••t. ........~ .... t••••••••••• ::. ••••••••••• J: ••••••••• -.. ••S.. .....................,_ _ _,_-'---~-'--' i ::) {;.$ (i.e. c.~: ::: ..: o .. ,:t:? i'ot»Mal 1,;;,_ C1,f» '°"NI Figure 3 U.S. Patent Dec. 1, 2020 Sheet 2 of 15 US 10,854,911 B2 3,7•0MeEPT- 0 -1,0 PotMtl~I \t$, Cp1 F$ -«'U {V} Figure 4 b H ....... f:PT ······· :~tf'.•OM.-:':!t:.?T i~~ .. t,.1M~£PT i,~.. f)M>15:-'fft"f 6-.:Y.) 70(; llOO W&>J~~!M1;11l"s (ili'rS} Figures Sa and Sb U.S. Patent Dec. 1, 2020 Sheet 3 of 15 US 10,854,911 B2 Figure 6 Figure 7 U.S. Patent Dec. 1, 2020 Sheet 4 of 15 US 10,854,911 B2 Hgure 8 Hgure 9 U.S. Patent Dec. 1, 2020 Sheet 5 of 15 US 10,854,911 B2 Figure 10 EPT 1.0 {l5 0 Potential vs Cp F +JO -0,5 ' 2 e (V} Figure 11 U.S. Patent Dec. 1, 2020 Sheet 6 of 15 US 10,854,911 B2 1.' :i:'.~ . I ir•:::• ~ · ~ =❖-:::::. .../ ............ ----------------""""'-----···::-=·······=······=...=~,jl= t »1-:--, ,◊, ::-.';. ::~ :... ~ .J <:;·w s::: ' i .....',:::,:,:,::::::~:€;:!: ~ ' U.S. Patent Dec. 1, 2020 Sheet 7 of 15 US 10,854,911 B2 = u0 .::;··;-;:::~· .... ~ h~}"' df;-~ U.S. Patent Dec. 1, 2020 Sheet 8 of 15 US 10,854,911 B2 I :~ f:;,}, •.•.•,) l· ::8-.:. l1:f~-~:::··:>;l ~:~:•':<•·· t>,:··~•.;• -::~:··:>.; ~--:::·•:f ,:i:··~' ~:~:··:/ ❖~•:;::.: ~$··;,· ~:~::•:>.' i;">:·<<·1: ❖~::•:;.·, t=::··:>-' t-::··:~.' ~;~:>~i•,/ -:~:·:>~ ~:-:::··:~} ~~:>;::-• U.S. Patent Dec. 1, 2020 Sheet 9 of 15 US 10,854,911 B2 sc~~- ;_J_l--'. , , -- '"'"""'...,.....,....,.....,....,.....,....,.....,....,.....,....,. __0~-------AIJ.l(l!llllllllllllllllllllllllll"8\ . r~J ,s- •... J an-... ,,'?n---··' t·:::;:r-.:. ;t~t::'.: ;::~tt*H• U.S. Patent Dec. 1, 2020 Sheet 10 of 15 US 10,854,911 B2 r-,;;:,-~ "' ~4 •.. :~-... •... .-: .. are·~: l · ~e~· ~~ -:-·i ~•.•.mw.v.m~~~~~~~~~~--------••...-,•;,;,;,• ~- v U.S. Patent Dec. 1, 2020 Sheet 11 of 15 US 10,854,911 B2 .rtn··=-­ ,s·t•~·~.,,; 5··(:i~ .... U.S. Patent Dec. 1, 2020 Sheet 12 of 15 US 10,854,911 B2 U.S. Patent Dec. 1, 2020 Sheet 13 of 15 US 10,854,911 B2 z: Ii,. Q --·················l.J···=~-~--=· ,·•:/ii···.,· ?'•:}tT./ ~··········------=l *':,':(!.····' n:£J·-.... ;;:~~!······ U.S. Patent Dec. 1, 2020 Sheet 14 of 15 US 10,854,911 B2 ! ,., ........... ...:.'-'~~:::::·:::::r,.. ::;:::·:= ,. ......-,::::'.1·•$::·::• :<,%··"·••. q;;:.•:r· ;n1r~.,- .• ::r ,::,-,,•.•~ :;=:::::: U.S. Patent Dec. 1, 2020 Sheet 15 of 15 US 10,854,911 B2 :!-~ ·::::;,t [. :~ .·.·.·.·-·.·.·.·.·.·.·.·.·.·.·.·.·.·.·.·.·.·.·.·.··········"": •.1.::t~,.., 1~ ~ g r~:j :: ,;;,··;,;;--,;;--;;;--·,;.,--,;--·;;;--,,-,--;;;--·;;;--,;;--;;;--·,,-,--,;;--·;;;--,,-,--;;;--·=.,,.,.=---fl'~ g :: :~ i '~ +- i~ l::: ·----------et g ~?.::?:{>-:;, f.-::in·-·.·~ i fY(:.?.1-····;;­ ·, ...·- ...- ...~ ..- ...- ...- ..- ... -.,.-...- ...- ..- ...-.,.- ...- ..- .. -...- .. ------..:::::~ :. g t.i:":itl··_=. ;j 'M :\ ~~•;ff.·/ :; $,: it~O::?:t-~· ti~~./· (~ ~-~~----···· lIB !. § E I., :r 1-§ US 10,854,911 B2 1 2 1,9,10-SUBSTITUTED PHENOTHIAZINE overcharge protection has been demonstrated for lower­ 3 9 DERIVATIVES WITH STRAINED RADICAL voltage LiFePO4 cathodes,[ a. J which require shuttles that CATIONS AND USE THEREOF oxidize at potentials of 3.8 to 3.9 V vs. Li+m_ However, the protection of higher-voltage cathodes (i.e. LiCoO2 , PRIORITY 5 LiMnO2 , and LiNi113Mn113Co 113O2 ) require oxidation potentials of 4.2 V or higher, and no shuttle has provided extensive protection in cells containing graphitic anodes. This invention claims priority to U.S. Provisional Appli­ Maximizing both the energy density and the durability of cation Ser. No. 62/364,060 filed Jul. 19, 2016. a LIBs requires charging to a precise voltage: below that potential, the full capacity of the cell is not utilized; at higher 10 GOVERNMENT INTEREST potentials, a cell enters overcharge, a condition that can seriously degrade LIBs and lead to hazardous operating This invention was made with govermnent support under conditions. [3l grant number 1300653 awarded by the National Science The road to higher oxidation potential shuttles via the Foundation. The govermnent has certain rights in the inven­ incorporation of strong electron-withdrawing groups on tion. 15 viable low-voltage shuttles can introduce perils in the frame­ work of LIB s. Electron-withdrawing substituents shift both TECHNICAL FIELD the oxidation and reduction potentials to more positive values, producing compounds that are more susceptible to The presently-disclosed subject
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