US009853270B2 (12 ) United States Patent ( 10 ) Patent No. : US 9 ,853 , 270 B2 Alkordi et al. ( 45) Date of Patent: Dec. 26 , 2017 (54 ) NANOSTRUCTURED METAL ORGANIC HO1M 4 / 24 ; H01M 4 /64 ; HO1M 2 / 1673 ; MATERIAL ELECTRODE SEPARATORS AND HO1M 2 / 1653; HO1M 2 /145 ; HOLM METHODS THEREFOR 10 /04 ; Y10T 29 / 49115 See application file for complete search history . @(71 ) Applicant: KING ABDULLAH UNIVERSITY OF SCIENCE AND TECHNOLOGY , (56 ) References Cited Thuwal (SA ) U . S . PATENT DOCUMENTS @( 72 ) Inventors : Mohamed Helmi Alkordi, Thuwal 5 , 378 ,571 A 1 / 1995 Macholdt ( SA ) ; Mohamed Eddaoudi, Thuwal 6 , 624, 318 B1 . 9 /2003 Mueller et al. (SA ) 6 , 893 , 564 B2 * 5 / 2005 Mueller et al. 210 /502 . 1 6 , 929 , 679 B2 8 / 2005 Mueller et al. ( 73 ) Assignee : King Abdullah University of Science 6 , 930 , 193 B2 8 / 2005 Yaghi et al. and Technology , Thuwal (SA ) 7 , 196 , 210 B2 3 /2007 Yaghi et al . 7 ,279 , 517 B2 10 / 2007 Mueller et al . ( * ) Notice : Subject to any disclaimer , the term of this 7 , 880 , 026 B2 2 / 2011 Ni et al. patent is extended or adjusted under 35 7 , 981 , 818 B2 7 / 2011 Justice U . S . C . 154 ( b ) by 507 days . (Continued ) ( 21) Appl . No. : 13/ 861 , 775 OTHER PUBLICATIONS (22 ) Filed : Apr. 12 , 2013 International Search Report and Written Opinion for PCT/ US2013 / 036329 dated Jul. 25 , 2013 . (65 65 ) Prior Publication Data (Continued ) US 2013 /0280611 A1 Oct . 24 , 2013 Primary Examiner — Raymond Alejandro Related U . S . Application Data ( 74 ) Attorney , Agent, or Firm — Billion & Armitage ; (60 ) Provisional application No . 61/ 625 , 973, filed on Apr. Benjamin Armitage 18 , 2012 . ( 57 ) ABSTRACT (51 ) Int. Ci. Provided herein are nanostructured electrode separators HOIM 4 /50 ( 2010 . 01 ) comprising metal organic materials capable of attaching to HOLM 2 / 16 ( 2006 .01 ) one or more electrodes and electrically insulating at least HOIM 2 / 14 ( 2006 .01 ) one electrode while allowing migration of ionic charge (52 ) U . S . CI. carriers through the nanostructured electrode separator. CPC .. HOIM 2 / 1673 (2013 . 01 ) ; HOIM 2 / 1653 Methods of using such electrode separators include posi (2013 .01 ) ; HOTM 4 / 50 (2013 .01 ) ; HOIM 2 / 145 tioning a nanostructured electrode separator between two (2013 .01 ) ; Y1OT 29/ 49115 (2015 .01 ) ( 58 ) Field of Classification Search electrodes of an electrochemical cell . CPC . .. .. .. .. HO1M 4 /50 ; HOTM 4 / 13 ; HO1M 4 / 14 ; 17 Claims, 13 Drawing Sheets US 9 ,853 ,270 B2 Page 2 (56 ) References Cited U . S . PATENT DOCUMENTS 8 , 034 , 952 B2 10 / 2011 Eddaoudi et al. 8 , 119 , 295 B2 2 / 2012 Drew et al. 8 , 123 , 834 B2 2 / 2012 Masel et al. 8 ,680 , 231 B2 3 / 2014 Po et al . 2003 /0222023 Al 12 / 2003 Mueller et al. 2009 /0148760 AL 6 / 2009 Justice 2009 /0305040 A1 * 12 / 2009 Schubert et al . 428 / 402 2010 /0132547 A1 6 / 2010 Masel et al . 2010 /0266897 A1 * 10 / 2010 Lee .. .. .. .. B82Y 10 /00 429 /219 2011/ 0139331 A1 6 / 2011 Arora et al. 2011 /0143173 AL 6 / 2011 Drew et al. 2011/ 0287316 A1 * 11 /2011 Lu . .. B82Y 30 / 00 429 /215 2011/ 0319573 Al 12 /2011 Po et al. 2012 / 0003475 A1 * 1 / 2012 Benin et al . 428/ 402 2012 /0028086 A12 / 2012 Shi et al . 2012 /0077092 A1 * 3 / 2012 Lee et al . 429 / 307 2012 /0082884 A1 4 / 2012 Orilall et al. 2013/ 0115453 A1 * 5 /2013 Fan . .. .. .. HO5K 1 /0213 428 /372 OTHER PUBLICATIONS International Preliminary Report on Patentability for PCT /US2013 / 036329 dated Oct. 21, 2014 . Kundu , et al ., “ Alkali earth metal (Ca , Sr, Ba ) based thermostable metal- organic frameworks (MOFs ) for proton conduction ” , Chem . Commun . , 2012 , 48 , pp . 4998 - 5000 ., Mar. 27 , 2012 . * cited by examiner U . S . Patent Dec . 26 , 2017 Sheet 1 of 13 US 9 ,853 , 270 B2 Anode Separator, e. g . MOF/ CP /COFI Cathode Fig . 1 U . S . Patent Dec . 26 , 2017 Sheet 2 of 13 US 9 ,853 , 270 B2 Bridging group Polyvalent core Fig . 2A BridgingBridging group w Polyvalent core Fig . 2B Bridging group Polyvalent core Fig . 2C U . S . Patent Dec . 26 , 2017 Sheet 3 of 13 US 9 ,853 , 270 B2 Fig . 3A Fig . 3B U . S . Patent Dec. 26 , 2017 Sheet 4 of 13 US 9 ,853 , 270 B2 * * SENSEO World Lien 2009 Sept 2 . 8 199 200 * * Dia Fig . 4A k Te * S 3333 ]. Quan Fig . 4B U . S . Patent Dec. 26 , 2017 Sheet 5 of 13 US 9 ,853 ,270 B2 OFX Fig . 5A 65 um Sx w wwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwww Fig . 5B U . S . 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Patent Dec . 26 , 2017 Sheet 12 of 13 US 9 ,853 ,270 B2 QWx X258 * * * * * * KA Y * * * * * * * * * * ? ? ? ? ? 2x Fig . 12A ieenisinin 80 um Cox MAAK WSSSSSSSSSSSSSSSSS NEN Fig . 12B U . S . Patent Dec . 26 , 2017 Sheet 13 of 13 US 9 ,853 ,270 B2 COF www Alisuoju)Bagajos estimentosenlosentreelementos va: VW comment mentionnel e tiserende diesen times in del nostre te nen una entitate con la sensitie we ooreenkomsten . 5 10 15 20 25 30 35 40 45 29* Fig . 13 US 9 ,853 , 270 B2 NANOSTRUCTURED METAL ORGANIC Other aspects, embodiments , and features will be apparent MATERIAL ELECTRODE SEPARATORS AND from the following description , the drawings, and the METHODS THEREFOR claims. CLAIM OF PRIORITY DESCRIPTION OF DRAWINGS This application claims the benefit of prior U . S . Provi FIG . 1 is a diagram illustrating a portion of a battery or an sional Application No . 61 /625 ,973 , filed on Apr. 18 , 2012 , electrochemical cell. which is incorporated by reference in its entirety . FIGS. 2A , 2B and 2C are diagrams illustrating a lattice 10 structure that can be built to create a nanostructured sepa TECHNICAL FIELD rator. FIGS . 3A and 3B are photographs of electrode pellet and or use in nanostructured separator coated electrode pellet . This invention relates to an electrode separator for use in nanFIGS . 4A and 4B are micrograph images of electrode a battery or an electrochemical cell. 15 pellet and nanostructure separator coated electrode pellet. FIGS . 5A and 5B are micrograph images of electrode BACKGROUND pellet and nanostructured separator coated electrode pellet. FIG . 6 is a graph depicting the X -ray powder diffraction Batteries and electrochemical cells can be used as sources pattern of the nanostructured separator on the electrode of energy . Generally, batteries and electrochemical cells 20 pellet . include a positive electrode , a negative electrode , a separator FIG . 7 is a diagram depicting the X - ray crystal structure between the positive electrode and the negative electrode of the nanostructured separator on the electrode pellet . that prevents electrical contact between the two electrodes , FIGS . 8A and 8B are photographs of electrode pellet and and an electrolytic solution in contact with the electrodes nanostructured separator coated electrode pellet . and separator that permits ion migration . Electrons flow 25 FIGS . 9A and 9B are micrograph images of electrode from electrode to electrode via a conductor. The physical pellet and nanostructured separator coated electrode pellet. and chemical properties of the separator can affect the FIG . 10 is a graph depicting the X - ray powder diffraction performance properties of the battery or electrochemical pattern of the nanostructured separator on the electrode cell . pellet . 30 FIG . 11 is a diagram depicting the X - ray crystal structure SUMMARY of the nanostructured separator on the electrode pellet . FIGS . 12A and 12B are micrograph images of the surface A separator for a battery or electrochemical cell can be a of an electrode pellet after pellet -press of a nanostructured nanostructured separator. separator. In one aspect, an electrode material includes an electrode 35 FIG . 13 is a graph depicting the X - ray powder diffraction substrate and a nanostructured separator on a surface of the pattern of the nanostructured separator on the electrode electrode substrate . pellet. In another aspect , an electrochemical cell comprising an DETAILED DESCRIPTION electrode substrate , a nanostructured separator on a surface 40 of the electrode substrate and a second electrode in contact Referring to FIG . 1 , a battery or electrochemical cell can with the nanostructured separator. include a cathode , an anode and a separator between the In another aspect, a method of forming an electrode cathode and anode . The battery or electrochemical cell can material includes forming the nanostructured separator on a be contained within a suitable housing (not shown ). surface of the electrode support . 45 The battery and electrochemical cell include a primary In another aspect, a method of forming an electrochemical cell or a non - rechargeable battery or a secondary cell or cell includes forming the nanostructured separator on a rechargeable battery . Examples of a primary cell includes an surface of the electrode support and contacting the nano alkaline battery , aluminum battery , chromic acid cell , Clark structured separator with the second electrode .