( 12 ) United States Patent
`Li et al .
`
`( 10 ) Patent No .: US 10,675,819 B2
`( 45 ) Date of Patent :
`* Jun . 9 , 2020
`
`US010675819B2
`
`( 54 ) MAGNETIC FIELD ALIGNMENT OF
`EMULSIONS TO PRODUCE POROUS
`ARTICLES
`( 71 ) Applicants : Massachusetts Institute of
`Technology , Cambridge , MA ( US ) ;
`Northeastern University , Boston , MA
`( US )
`( 72 ) Inventors : Linsen Li , Malden , MA ( US ) ;
`Jonathan Samuel Sander , Zurich
`( CH ) ; Yet - Ming Chiang , Weston , MA
`( US ) ; Randall Morgan Erb , Newton ,
`MA ( US )
`( 73 ) Assignees : Massachusetts Institute of
`Technology , Cambridge , MA ( US ) ;
`Northeastern University , Boston , MA
`( US )
`Subject to any disclaimer , the term of this
`patent is extended or adjusted under 35
`U.S.C. 154 ( b ) by 687 days .
`This patent is subject to a terminal dis
`claimer .
`( 21 ) Appl . No .: 15 / 390,295
`( 22 ) Filed :
`Dec. 23 , 2016
`( 65 )
`Prior Publication Data
`US 2017/0173893 A1 Jun . 22 , 2017
`
`( * ) Notice :
`
`Related U.S. Application Data
`( 63 ) Continuation - in - part of application No. 14 / 874,253 ,
`filed on Oct. 2 , 2015 .
`( Continued )
`
`( 51 )
`
`Int . Ci .
`B29C 67/20
`BO3C 1/32
`
`( 2006.01 )
`( 2006.01 )
`( Continued )
`
`( 58 )
`
`( 52 ) U.S. CI .
`B29C 67/202 ( 2013.01 ) ; B03C 1/32
`CPC
`( 2013.01 ) ; H01F 1/447 ( 2013.01 ) ; HOTM 4/04
`( 2013.01 ) ;
`( Continued )
`Field of Classification Search
`B29C 67/202
`CPC
`See application file for complete search history .
`References Cited
`U.S. PATENT DOCUMENTS
`
`( 56 )
`
`CA
`CA
`
`3,284,243 A
`3,765,943 A
`
`11/1966 Von Sturm
`10/1973 Biagetti
`( Continued )
`FOREIGN PATENT DOCUMENTS
`2270771
`10/2000
`2426156 C
`4/2011
`( Continued )
`OTHER PUBLICATIONS
`International Search Report and Written Opinion in International
`Patent Application No. PCT / US2015 / 053761 , dated Feb. 18 , 2016 .
`( Continued )
`Primary Examiner Monica A Huson
`Assistant Examiner — Kelsey C Grace
`( 74 ) Attorney , Agent , or Firm
`Wolf , Greenfield &
`Sacks , P.C.
`( 57 )
`ABSTRACT
`The use of magnetic fields in the production of porous
`articles is generally described . Certain embodiments are
`related to methods of producing porous articles in which
`magnetic fields are applied to an emulsion to align emulsion
`droplets . In some embodiments , after the emulsion droplets
`have been aligned , the emulsion droplets and / or the medium
`surrounding the emulsion droplets can be removed to leave
`behind a porous article . According to certain embodiments ,
`polyvinyl alcohol can be used , for example , to stabilize the
`( Continued )
`
`oo
`
`Solvent evaporation
`
`3200
`
`Large fugitive perrofluid
`emulsion
`droplets
`
`LUMENIS EX1009
`Page 1
`
`

`

`US 10,675,819 B2
`Page 2
`
`emulsion droplets and / or bind together components of the
`porous article . In some embodiments , water - soluble liquid
`alcohol can be used , for example , to stabilize the suspension
`of electronically conductive material within a phase of the
`emulsion .
`
`20 Claims , 18 Drawing Sheets
`
`Related U.S. Application Data
`( 60 ) Provisional application No. 62 / 347,475 , filed on Jun .
`8 , 2016 , provisional application No. 62 / 217,554 , filed
`on Sep. 11 , 2015 , provisional application No.
`62 / 059,315 , filed on Oct. 3 , 2014 .
`( 51 ) Int . Ci .
`HOIM 4/525
`HOIM 4/62
`HOIM 4/04
`HOIF 1/44
`HOIM 4/131
`HOIM 4/505
`HOIM 4/1391
`HOIM 4/587
`B29K 29/00
`B29K 105/00
`B29L 31/34
`HOIM 4/02
`( 52 ) U.S. CI .
`???
`
`( 2010.01 )
`( 2006.01 )
`( 2006.01 )
`( 2006.01 )
`( 2010.01 )
`( 2010.01 )
`( 2010.01 )
`( 2010.01 )
`( 2006.01 )
`( 2006.01 )
`( 2006.01 )
`( 2006.01 )
`
`HOIM 4/131 ( 2013.01 ) ; HOIM 4/1391
`( 2013.01 ) ; HOTM 4/505 ( 2013.01 ) ; HOIM
`4/525 ( 2013.01 ) ; HOTM 4/587 ( 2013.01 ) ;
`HOIM 4/623 ( 2013.01 ) ; HOTM 4/625
`( 2013.01 ) ; B29K 2029/04 ( 2013.01 ) ; B29K
`2105/0064 ( 2013.01 ) ; B29K 2995/0005
`( 2013.01 ) ; B29K 2995/0008 ( 2013.01 ) ; B29L
`2031/3468 ( 2013.01 ) ; HOIM 2004/021
`( 2013.01 )
`
`( 56 )
`
`References Cited
`U.S. PATENT DOCUMENTS
`2/1975 Broadbead et al .
`3,864,167 A
`1/1981 Rampel
`4,245,016 A
`4,555,454 A
`11/1985 Shuster et al .
`4/1986 Jaisinghani et al .
`4,579,637 A
`7/1986 Atkinson
`4,599,114 A
`4,615,784 A
`10/1986 Stewart et al .
`4,668,596 A
`5/1987 Shacklette et al .
`7/1988 Armand et al .
`4,758,483 A
`2/1989 Vanderborgh et al .
`4,804,592 A
`4,889,777 A
`12/1989 Akuto
`3/1992 Hayashida et al .
`5,100,747 A
`2/1993 Hirai et al .
`5,187,209 A
`5,213,895 A
`5/1993 Hirai et al .
`7/1993 Goebel et al .
`5,227,267 A
`3/1994 Otagawa et al .
`5,294,504 A
`5,338,625 A
`8/1994 Bates et al .
`3/1995 Chaloner - Gill et al .
`5,399,447 A
`4/1995 Lemaire et al .
`5,405,937 A
`7/1995 Huang et al .
`5,436,093 A
`5,441,830 A
`8/1995 Moulton et al .
`5,464,707 A
`11/1995 Moulton et al .
`12/1995 Turi et al .
`5,478,676 A
`5/1996 Repplinger et al .
`5,518,833 A
`5,520,850 A
`5/1996 Chaloner - Gill et al .
`5,527,641 A
`6/1996 Koshiishi et al .
`5,554,459 A
`9/1996 Gozdz et al .
`
`5,567,754 A
`5,578,396 A
`5,587,253 A
`5,588,971 A
`5,589,297 A
`5,591,544 A
`5,624,605 A
`5,635,138 A
`5,645,781 A
`5,654,115 A
`5,677,080 A
`5,698,342 A
`5,705,291 A
`5,714,053 A
`5,733,683 A
`5,759,714 A
`5,769,996 A
`5,789,100 A
`5,821,033 A
`5,827,615 A
`5,834,136 A
`5,840,087 A
`5,843,292 A
`5,846,675 A
`5,888,670 A
`5,897,522 A
`5,902,689 A
`5,910,382 A
`5,925,283 A
`5,949,213 A
`6,063,519 A
`6,063,525 A
`6,069,221 A
`RE36,843 E
`6,096,453 A
`6,096,454 A
`6,096,494 A
`6,117,593 A
`6,120,940 A
`6,136,476 A
`6,156,453 A
`6,159,389 A
`6,174,623 B1
`6,190,798 B1
`6,231,779 B1
`6,242,124 B1
`6,280,875 B1
`6,280,879 B1
`6,287,720 B1
`6,291,097 B1
`6,300,016 B1
`6,306,540 B1
`6,322,924 B1
`6,337,156 B1
`6,342,317 B1
`6,358,645 B1
`6,376,393 B1
`6,395,429 B1
`6,403,263 B1
`6,410,189 B1
`6,413,284 B1
`6,413,285 B1
`6,432,585 B1
`6,451,487 B1
`6,454,977 B1
`6,495,283 B1
`6,511,780 B1
`6,528,033 B1
`6,555,268 B1
`6,565,763 B1
`6,599,662 B1
`6,645,675 B1
`6,664,006 B1
`6,730,438 B2
`6,753,111 B2
`6,764,525 B1
`6,783,894 B2
`6,787,232 B1
`6,797,435 B2
`
`10/1996 Stramel
`11/1996 Fauteux et al .
`12/1996 Gozdz et al .
`12/1996 Fauteux et al .
`12/1996 Koga et al .
`1/1997 Fauteux et al .
`4/1997 Cao et al .
`6/1997 Amatucci et al .
`7/1997 Popovic'et al .
`8/1997 Hasebe et al .
`10/1997 Chen
`12/1997 Klein
`1/1998 Amatucci et al .
`2/1998 Howard et al .
`3/1998 Searson et al .
`6/1998 Matsufuji et al .
`6/1998 McArdle et al .
`8/1998 Burroughs et al .
`10/1998 Cromack et al .
`10/1998 Touhsaent et al .
`11/1998 Gao et al .
`11/1998 Gozdz et al .
`12/1998 Spiros
`12/1998 Sazhin et al .
`3/1999 Kawakami
`4/1999 Nitzan
`5/1999 Vleggar et al .
`6/1999 Goodenough et al .
`7/1999 Taniuchi et al .
`9/1999 Lanni
`5/2000 Barker et al .
`5/2000 LaFollette
`5/2000 Chasser et al .
`8/2000 Lake et al .
`8/2000 Grunwald
`8/2000 Tran et al .
`8/2000 Tang et al .
`9/2000 Stachoviak et al .
`9/2000 Poehler et al .
`10/2000 Schutts et al .
`12/2000 Shimizu et al .
`12/2000 Miura et al .
`1/2001 Shackle
`2/2001 Okada et al .
`5/2001 Chiang et al .
`6/2001 Saito et al .
`8/2001 Kwak et al .
`8/2001 Andersen et al .
`9/2001 Yamashita et al .
`9/2001 Barker et al .
`10/2001 Jan et al .
`10/2001 Hiroi et al .
`11/2001 Hirahara et al .
`1/2002 Narang et al .
`1/2002 Patel et al .
`3/2002 Furukawa et al .
`4/2002 Newton et al .
`5/2002 Kang et al .
`6/2002 Roach
`6/2002 Yamada et al .
`7/2002 Chu et al .
`7/2002 Chu et al .
`8/2002 Kawakami et al .
`9/2002 Besner et al .
`9/2002 Kwok et al .
`12/2002 Yoon et al .
`1/2003 Veregin et al .
`3/2003 Barker et al .
`4/2003 Inoue et al .
`5/2003 Asakawa et al .
`7/2003 Chiang et al .
`11/2003 Munshi
`12/2003 Munshi
`5/2004 Nakanishi et al .
`6/2004 Kweon et al .
`7/2004 Whitacre et al .
`8/2004 Kajiura et al .
`9/2004 Chiang et al .
`9/2004 Kweon et al .
`
`LUMENIS EX1009
`Page 2
`
`

`

`( 56 )
`
`References Cited
`U.S. PATENT DOCUMENTS
`6,800,399 B2
`6,818,356 B1
`6,844,105 B1
`6,855,273 B2
`6,878,487 B2
`6,982,132 B1
`7,026,071 B2
`7,033,702 B2
`7,087,348 B2
`7,090,785 B2
`7,318,982 B2
`7,338,734 B2
`7,387,851 B2
`7,553,584 B2
`7,579,112 B2
`7,662,265 B2
`7,763,382 B2
`7,781,098 B2
`7,988,746 B2
`8,148,009 B2
`8,168,326 B2
`8,277,975 B2
`9,065,093 B2
`10,164,242 B2
`2001/0005558 Al
`2001/0005562 A1
`2001/0007726 A1
`2001/0043709 Al
`2002/0000034 Al
`2002/0015278 A1
`2002/0028380 A1
`2002/0036282 A1
`2002/0048706 A1
`2002/0071990 A1
`2002/0071991 Al
`2002/0074972 A1
`2002/0192137 Al
`2002/0195591 Al
`2003/0003352 A1
`2003/0008212 Al
`2003/0049529 A1
`2003/0054250 A1
`2003/0082446 Al
`2003/0099884 A1
`2003/0114297 A1
`2004/0005265 A1
`2004/0018429 A1
`2004/0018430 A1
`2004/0018431 Al
`2004/0151887 Al
`2004/0185343 A1
`2004/0265692 A1
`2005/0026037 Al
`2005/0034993 Al
`2005/0048374 A1
`2005/0082726 A1
`2005/0175529 Al
`2005/0181280 A1
`2005/0272214 A1
`2006/0035143 A1
`2006/0102455 A1
`2006/0234131 A1
`2007/0009801 A1
`2007/0275300 A1
`2008/0099734 Al
`2008/0213662 A1
`2008/0254368 A1
`2008/0292862 Al
`2008/0311470 A1
`2009/0035664 A1
`2009/0202903 Al
`2009/0235520 A1
`2009/0253025 Al
`2010/0003603 Al
`2010/0092867 A1
`
`10/2004 Matsumoto
`11/2004 Bates
`1/2005 Hanafusa et al .
`2/2005 Ravet et al .
`4/2005 Cho et al .
`1/2006 Goldner et al .
`4/2006 Mayes et al .
`4/2006 Dasgupta et al .
`8/2006 Holman et al .
`8/2006 Chiang et al .
`1/2008 Gozdz et al .
`3/2008 Chiang et al .
`6/2008 Gozdz et al .
`6/2009 Chiang et al .
`8/2009 Chiang et al .
`2/2010 Chiang et al .
`7/2010 Riley et al .
`8/2010 Chiang et al .
`8/2011 Chiang et al .
`4/2012 Chiang et al .
`5/2012 Chiang et al .
`10/2012 Chiang et al .
`6/2015 Chiang et al .
`12/2018 Chiang et al .
`6/2001 Yoshioka et al .
`6/2001 Yoshioka et al .
`7/2001 Yoshioka et al .
`11/2001 Panitzsch
`1/2002 Jensen
`2/2002 Fukuyama et al .
`3/2002 Tanjo et al .
`3/2002 Chiang et al .
`4/2002 Mayes et al .
`6/2002 Kweon et al .
`6/2002 Kweon et al .
`6/2002 Narang et al .
`12/2002 Chaloner - Gill et al .
`12/2002 Ravet et al .
`1/2003 Kweon et al .
`1/2003 Akashi et al .
`3/2003 Cho et al .
`3/2003 Kweon et al .
`5/2003 Chiang et al .
`5/2003 Chiang et al .
`6/2003 Shinn et al .
`1/2004 Chiang et al .
`1/2004 Kweon et al .
`1/2004 Holman et al .
`1/2004 Gozdz et al .
`8/2004 Forrest et al .
`9/2004 Wang et al .
`12/2004 Long et al .
`2/2005 Riley , Jr. et al .
`2/2005 Gozdz et al .
`3/2005 Yonezawa
`4/2005 Hilmas et al .
`8/2005 Ceder et al .
`8/2005 Ceder et al .
`12/2005 Chiang et al .
`2/2006 Kida et al .
`5/2006 Chiang et al .
`10/2006 Takami et al .
`1/2007 Inagaki et al .
`11/2007 Salot et al .
`5/2008 Chiang et al .
`9/2008 Chiang et al .
`10/2008 Ooyama et al .
`11/2008 Filippov et al .
`12/2008 Gozdz et al .
`2/2009 Chiang et al .
`8/2009 Chiang et al .
`9/2009 Atsumi et al .
`10/2009 Whitacre
`1/2010 Chiang et al .
`4/2010 Lau et al .
`
`US 10,675,819 B2
`Page 3
`
`2010/0248028 Al
`2011/0005065 A1
`2011/0038656 Al
`2011/0045346 A1
`2011/0070489 A1
`2011/0097623 A1
`2011/0151324 Al
`2011/0278170 A1
`2012/0315538 Al
`2015/0364753 Al
`2016/0096334 A1 *
`
`9/2010 Riley et al .
`1/2011 Chiang et al .
`2/2011 Chiang et al .
`2/2011 Chiang et al .
`3/2011 Chiang et al .
`4/2011 Chiang et al .
`6/2011 Chiang et al .
`11/2011 Chiang et al .
`12/2012 Chiang et al .
`12/2015 Chiang et al .
`4/2016 Sander
`
`2017/0087074 A1 *
`
`3/2017 Perusse
`
`B29C 67/202
`264/427
`A61K 8/416
`
`FOREIGN PATENT DOCUMENTS
`
`CN
`CN
`CN
`DE
`EP
`EP
`EP
`EP
`EP
`EP
`EP
`EP
`GB
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`KR
`KR
`WO
`WO
`WO
`WO
`WO
`WO
`WO
`WO
`
`1470083 A
`1901255 A
`1945881 A
`102007042217 A
`0 757 407 A1
`967672 A1
`1 113 511 A1
`1 042 832 A1
`1 184 918
`1 231 651
`1 231 653
`1 860 722 A1
`976971
`53-98038
`55-010738 A
`59-094379
`59-152565 A
`60-183365 A
`61-4167 A
`63-121272 A
`63-289768
`04-58455
`05-029006
`05-041211 A
`05-109429
`60-104167 A
`06-236768 A
`71-01728 A
`07-153492 A
`07-262986 A
`08-138650 A
`08-321306 A
`09-022693 A
`09-147862
`09-298057 A
`09-320569 A
`11-121006
`11-121025 A
`11-121061
`11-154508
`11-162519 A
`2000-021415 A
`2000-045639 A
`2000-080406 A
`2000-106213
`2000-173645 A
`2000-195525 A
`2000-195526 A
`2000-228213 A
`2000-248095 A
`2001-151834
`2002-151055 A
`4-206366 B2
`1019910007466
`1998-071228
`WO 97/05666 A2
`WO 97/27635 A1
`WO 97/44843
`WO 98/12761 A1
`WO 98/16960 A2
`WO 98/48466 Al
`WO 99/33129 A1
`WO 99/56331 Al
`
`1/2004
`1/2007
`4/2007
`3/2009
`2/1997
`12/1999
`7/2001
`10/2001
`3/2002
`8/2002
`8/2002
`8/2002
`12/1964
`8/1978
`1/1980
`5/1984
`8/1984
`9/1985
`1/1986
`5/1988
`11/1988
`2/1992
`2/1993
`2/1993
`4/1993
`4/1994
`8/1994
`4/1995
`6/1995
`10/1995
`5/1996
`12/1996
`1/1997
`6/1997
`11/1997
`12/1997
`4/1999
`4/1999
`4/1999
`6/1999
`6/1999
`1/2000
`2/2000
`3/2000
`4/2000
`6/2000
`7/2000
`7/2000
`8/2000
`9/2000
`6/2001
`5/2002
`1/2009
`9/1991
`10/1998
`2/1997
`7/1997
`11/1997
`3/1998
`4/1998
`10/1998
`7/1999
`11/1999
`
`LUMENIS EX1009
`Page 3
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`( 56 )
`
`WO
`WO
`WO
`WO
`WO
`WO
`WO
`WO
`WO
`WO
`WO
`WO
`
`References Cited
`FOREIGN PATENT DOCUMENTS
`
`WO 00/10736 A1
`WO 00/41256 A1
`WO 01/77501 A2
`WO 02/43168 A2
`WO 03/012908 A2
`WO 03/056646 A1
`WO 07/028972 A1
`WO 08/011061 Al
`WO 08/153749
`WO 2013/112670 A1
`WO 14/170024 Al
`WO 2016/054530 A1
`
`3/2000
`7/2000
`10/2001
`5/2002
`2/2003
`7/2003
`3/2007
`1/2008
`12/2008
`8/2013
`10/2014
`4/2016
`
`OTHER PUBLICATIONS
`Aleshin , A.N. et al . , “ Transport Properties of Poly ( 3,4
`Ethylenedioxythiophene ) / Poly ( Styrenesulfonate ) , ” Synthetic Met
`als 94 : 173-7 ( 1998 ) .
`Allen , J.L. , et al . , “ LI1 + xFE1 - P04 : Electronically conductive Lithium
`Iron Phospho - olivines with Improved Electrochemical Perfor
`mance , ” The Proceedings of The Electrochemical Society 28 : 198
`205 ( 2003 ) .
`Arbizzani et al , “ Li1.01Mn1.974 surface modification by pol ( 3,4
`ethylenedioxythiophene ) , ” J. Power Sources , 2003 ; 119-121 : 695
`700 .
`Arbizzani et al . , “ L11.03 Mn1.9704 Surface Modification by Poly
`( 3,4 - Ethylenedioxithiophene ) , ” Poster presented at 11th Intl . Meet
`ing on Lithium Batteries , Jun . 23-28 , 2002 , Monterey , CA.
`Armand et al . , Conjugated dicarboxylate anodes for Li - ion batteries .
`Nature Materials Jan. 18 , 2009. 8 : 120-5 . DOI : 10.1038 / nmat2372 .
`Armand , M.B. et al . , “ Poly - Ethers as Solid Electrolytes , ” Proceed
`ings of the Intl . Conference on Fast Ion Transport in Solids ,
`Electrodes and Electrolytes , Lake Geneva , WI , 131-136 ( 1979 ) .
`Bae et al . , Design of Battery Electrodes with Dual - Scale Porosity to
`Minimize Tortuosity and Maximize Performance . Advanced Mate
`rials . 2012. 5 pages . DOI : 10.1002 / adma.201204055 .
`Bae et al . , High density sintered electrode architecture to improve
`the energy density of rechargeable lithium batteries . Poster pre
`sented Jul . 1 , 2010 at the 15th International Meeting on Lithium
`Batteries , Jun . 27 - Jul . 2 , 2010. Montreal , Quebec , Canada . 1 page .
`Bae et al . , Influence of controlled pore topology in sintered Li - ion
`battery cathodes on electrochemical performance . Presented at the
`Materials Research Society fall meeting in Nov. 2010. 18 pages .
`Bervas et al . , Investigation of the Lithiation and Delithiation Con
`version Mechanisms in a Bismuth Fluoride Nanocomposites . J.
`Electrochem . Soc . Mar. 2 , 2006. 153 ( 4 ) : A799-808 .
`Bouridah , A. et al . , “ Poly ( Dimethylsiloxane ) -Poly ( Ethylene Oxide )
`Based Polyurethane Networks Used as Electrolytes in Lithium
`Electrochemical Solid State Batteries , ” Solid State Ionics , 15 ( 1985 )
`pp . 233-240 .
`Broadhead et al . , Chapter 2. Electrochemical Principles and Reac
`tions . Handbook of Batteries . 1995 : 2.1-2.35 .
`Cernak et al . , Aggregation dynamics of nonmagnetic particles in a
`ferrofluid . Physical Review E. Sep. 29 , 2004 ; 70 ( 3 ) : 031504 .
`Chan et al , High - performance lithium battery anodes using silicon
`nanowires . Nature Nanotechnology . 2008. 3 : 31-5 . Doi : 10.1038 /
`nnano.2007.411 . Published online Dec. 16 , 2007 .
`Chen et al . , Reducing Carbon in LiFePO4 / C Composite Electrodes
`to Maximize Specific Energy , Volumetric Energy , and Tap Density .
`J Electrochem Soc . 2002 ; 148 ( 9 ) : A1184-89 .
`Chen - Wiegart et al . , “ Tortuosity characterization of 3D microstruc
`ture at nano - scale for energy storage and conversion materials , ”
`Journal of Power Sources . 2014 ; 249 : 349-56 .
`Chiang et al . , Electrode architectures for enhancing energy density
`in rechargeable lithium batteries . Spring MRS Meeting Invited Talk
`Abstract . Abstract available prior to Apr. 7 , 2010. San Francisco ,
`California . 1 page .
`Chiang et al . , High Energy Density Low Tortuosity Battery Elec
`trodes and Methods of Manufacture . MIT . Apr. 7 , 2011. 12 pages .
`
`Chiang , Aligned ( Unit Tortuosity ) Porosity : 3 approaches using a
`removable ( fugitive ) pore former . Presentation slideshow accom
`panying talk given at Spring MRS Meeting Invited Talk . Apr. 7 ,
`2010. No handouts were distributed . 11 pages .
`Chiang , Y.-M. et al . , “ High Capacity , Temperature - Stable Lithium
`Aluminum Manganese Oxide Cathodes for Rechargeable Batter
`ies , ” Electrochem Sol St Lett , 2 ( 3 ) ( 1999 ) pp . 107-110 .
`Chiang , Design and Scalable Assembly of High Density Low
`Tortuosity Electrodes . Massachusetts Institute of Technology , Cam
`bridge , MA . Jun . 9 , 2016. Believed to have been distributed on May
`9 , 2016. Presented on Jun . 9 , 2016 .
`Chiang , Design and Scalable Assembly of High Density Low
`Tortuosity Electrodes . Massachusetts Institute of Technology . Cam
`bridge , MA . Jun . 17 , 2015. Believed to have been distributed on
`May 1 , 2015. Presented on Jun . 17 , 2015 .
`Cho et al . , Self - Assembling Colloidal - Scale Devices : Selecting and
`Using Short - Range Surface Forces Between Conductive Solids .
`Adv Funct Matter . 2007 ; 17 : 379-89 .
`Choi et al . , Determination of electrochemical active area of porous
`Li1 - C002 electrode using the GITT technique . Solid State Ionics .
`1998 ; 109 : 159-63 .
`Chung et al . , Validity of Bruggeman relation for porous electrodes .
`Modelling and Simulation in Materials Science and Engineering .
`2013 ; 21 : 1-16 .
`Darling et al . , Modeling a Porous Intercalation Electrode with Two
`Characteristic Particle Sizes . J Electrochem Soc . 1997 ; 144 : 4201-08 .
`Darling et al . , Modeling Side Reactions in Composite Li , Mn204
`Electrodes . J Electrochem Soc . 1998 ; 145 : 990-98 .
`Doyle et al . , Analysis of capacity - rate data for lithium batteries
`using simplified models of the discharge process . J Appl Electrochem .
`1997 ; 27 : 846-56 .
`Doyle et al . , Modeling of Galvanostatic Charge and Discharge of
`the Lithium Polymer / Insertion Cell . J Electrochem Soc . 1993 ; 140 : 1526
`33 .
`Doyle , Design and Simulation of Lithium Recharageable Batteris .
`Ph.D. Thesis . Unversity of California , Berkeley . 1995. 370 pages .
`Ehrlich , Chapter 35. Lithium - Ion Batteries . Handbook of Batteries .
`3rd ed . 2002 : 35.1 .
`Elliott , S.R. , “ Physics of Amorphous Materials , ” Longman Group
`Limited . New York . 1984 .
`Erb et al . , Composites reinforced in three dimensions by using low
`magnetic fields . Science . Jan. 13 , 2012 ; 335 ( 6065 ) : 199-204 . Doi :
`10.1126 / science.1210822 .
`Erb et al . , Magnetic assembly of colloidal superstructures with
`multipole symmetry . Nature . Feb. 19 , 2009 ; 457 ( 7232 ) : 999-1002 .
`doi : 10.1038 / nature07766 .
`Erbet al . , Beyond diffusion - limited aggregation kinetics in microparticle
`suspensions . Physical Review E. Nov. 2 , 2009 ; 80 ( 5 ) : 051402 .
`Fermigier et al . , Structure evolution in a paramagnetic latex sus
`pension . J Colloid Interface Science . 1992 ; 154 ( 2 ) : 522-39 .
`Furst et al . , Permanently Linked Monodisperse Paramagnetic Chains .
`Langmuir . 1998 ; 14 ( 26 ) : 7334-36 .
`French , R.H. et al . , “ Full Spectral Calculation of Non - Retarded
`Hamaker Constants for Ceramic Systems from Interband Transition
`Strengths , ” Solid State Ionics 75 : 13-33 ( 1995 ) .
`French , R.H. et al . , “ Origins and Applications of London Dispersion
`Forces and Hamaker Constants in Ceramics , " J. Am . Ceram . Soc .
`83 ( 9 ) : 2117-46 ( 2000 ) .
`Fuller et al . , Simulation and Optimization of the Dual Lithium Ion
`Insertion Cell . J Electrochem Soc . 1994 ; 141 : 1-10 .
`Gaubicher et al . , Li / B - VOPO4 : A New 4 V System for Lithium
`Batteries . J Electrochem Soc . 1999 ; 146 ( 12 ) : 4375-79 .
`Ghosh , S. et al . , “ Supramolecular Self - Assembly for Enhanced
`Conductivity in Conjugated Polymer Blends : Ionic Crosslinking in
`Blends of Poly ( 3,4 , -Ethylenedioxythiophene ) -Poly ( Styrenesulfonate )
`and Poly ( vinylpyrrolidone ) , ” Adv . Mater . 10 ( 14 ) : 1097 ( 1998 ) .
`Gray , F.M. , “ Solid Polymer Electrolytes , ” VCH Publishers Inc. New
`York . ( 1991 ) .
`Guyomard et al . , Li Metal - Free Rechargeable LiMn204 / Carbon
`Cells : Their Understanding and Optimization . J Electrochem Soc .
`1992 ; 139 : 937-48 .
`Hadziioannou , et al . , “ Monocristaus de copolymeres trisequences
`styrene / isoprene / styrene presentant la structure cylindrique : I. Etude
`
`LUMENIS EX1009
`Page 4
`
`

`

`US 10,675,819 B2
`Page 5
`
`( 56 )
`
`References Cited
`OTHER PUBLICATIONS
`de l'orientation par diffraction des rayons X aux petits angles , "
`Colloid Poly Sci . , 257 : 15-22 , 1979 .
`Hart , B. W. , et al . , “ 3 - D Microbatteries , ” Electrochemistry Com
`munications 5 : 120-3 ( 2003 ) .
`Huang et al . , Approaching Theoretical Capacity of LiFePO4 at
`Room Temperature at High Rates . Electrochem Solid - State Letts .
`2001 ; 4 ( 10 ) : A170-72 .
`Idota , Y. et al . , “ Tin - Based Amorphous Oxide : A High - Capacity
`Lithium - Ion - Storage Material , ” Science , vol . 276 ( May 30 , 1997 )
`pp . 1395-1397 .
`Kuwabata , S. et al . , “ Charge - Discharge Properties of Composites of
`LiMn204 and Polypyrole as Positive Electrode Materials for 4 V
`Class of Rechargeable Li Batteries , ” Electrochimica Acta 44 ( 23
`26 ) : 4593-600 ( 1999 ) .
`Le Cras , F. et al . , “ Lithium intercalation in Li - Mg - Mn— and
`Li - Al - Mn— spinels , ” Solid State Ionics , 89 ( 1996 ) pp . 203
`213 .
`Li et al . , Li - Storage via Heterogeneous Reaction in Selected Binary
`Metal Fluorides and Oxides , Journal of the Electrochemical Society .
`Oct. 21 , 2004. 151 ( 11 ) : A1878-85 . doi : 10.1149 / 1.1801451 .
`Li et al . , Synthesis and properties of poly ( 2,5,8,11,14,17,20,23
`octaoxapentacosyl methacrylate ) -block - poly ( 4 - vinylpyridine ) .
`Makromol Chem . 1991 ; 192 : 3043-50 .
`Li et al . , Project ES071 : Design and Scalable Assembly of High
`Density Low Tortuosity Electrodes . Poster . Submitted on May 9 ,
`2016. Presented on Jun . 9 , 2016 .
`Limthongkul , P. et al . , “ Nanocomposite Li - Ion Battery Anodes
`Produced by the Partial Reduction of Mixed Oxides , ” Chem Mat , 13
`( 2001 ) pp . 2397-2402 .
`Linden , Editor - in - Chief , “ Handbook of Batteries , " Second Edition ,
`McGraw - Hill , Inc. , USA , 1995 ( no . month ) , p . 2. 19 .
`Long , J.W. , et al . , “ Three - Dimensional Battery Architectures , ”
`Chem . Rev. 104 ( 10 ) : 4463-92 ( 2004 ) .
`Matsumoto , O. , et al . , “ Ionic Conductivity of Dual - Phase Polymer
`Electrolytes Comprise of MBR - SBR Latex Films Swollen with
`Lithium Slat Solutions ” , J. Electrochem Soc . , vol . 141 , No. 8 , Aug.
`1994 , 1989-93 .
`Matsumoto , Osamu et al . , “ Vaporization of Graphite in Plasma Arc
`and Identification of C60 in the Deposit , ” J. Electrochem . Soc . , vol .
`139 , No. 1 , Jan. 1992 , L8-9 .
`Mazouzi et al . , High capacity and excellent cyclability of Nano
`Silicon / CB / CMC composite anode from tailored electrode prepa
`ration . 216th Electrochemical Society Meeting . 2009 : Abstract
`# 417 .
`Meredith et al . , II . Conduction in Heterogeneous Systems . In :
`Advances in Electrochemistry and Electrochemical Engineering .
`John Wiley & Sons . New York . 1962 ; 2 : 15-47 .
`Milling , A. et al . , “ Direct Measurement of Repulsive Van Der Waals
`Interactions Using an Atomic Force Microscope , ” J. Colloid &
`Interface Science 180 : 460-5 ( 1996 ) .
`Minett , M.G. et al , “ Polymeric Insertion Electrodes , ” Solid State
`Ionics , 28-30 ( 1988 ) , pp . 1192-1196 .
`Moon et al . , Production of highly aligned porous alumina ceramics
`by extruding prozen alumina / camphene body . Journal of European
`Ceramic Society . 2011 ; 31 : 1945-50 .
`Nagaoka , K. et al , “ High Ionic Conductivity in Poly ( dimethyl
`Siloxane - co - Ethylene Oxide ) Dissolving Lithium Perchlorate , ” J.
`Polymer Science . pp . 659-663 , vol . 22 , 1984 .
`Nagarajan et al . , A Mathematical Model for Intercalation Electrode
`Behavior . I. Effect of Particle - Size Distribution on Discharge Capac
`ity . J Electrochem Soc . 1998 ; 145 : 771-79 .
`Nakahara et al . , Rechargeable batteries with organic radical cath
`odes . Chemical Physical Letters . Jun . 27 , 2002. 359 ( 5-6 ) : 351-4 .
`Neumann et al . , “ Negative Hamaker Coefficients , ” Colloid and
`Polymer Science 257 ( 4 ) : 413-9 ( 1979 ) .
`Newman et al . , Theoretical Analysis of Current Distribution in
`Porous Electrodes . J Electrochem Soc . 1962 ; 109 : 1183-91 .
`
`Newman , Chapter 22. Porous Electrodes . In : Electrochemical Sys
`tems . 2nd Edition . Prentice Hall . Englewood Cliffs , New Jersey .
`1991 : 450-95 .
`Nishide et al . , Organic radical battery : nitroxide polymers as a
`cathode - active material . Chem . Phys . Lett . Electrochim . Acta . Nov.
`30 , 2004. 50 ( 2-3 ) : 827-31 . doi : 10.1016 / j.electacta.2004.02.052 .
`Ohzuku , Tsutomu et al . , “ Synthesis and Characterization of
`LiAlfrax ; 1 ; 4Nifrax ; 3 ; 402 ( R3m ) for Lithium - Ion ( Shuttlecock ) Batter
`ies , "
`J. Electrochem . Soc . , vol . 142 , No. 12 , Dec. 1995 , pp .
`4033-4039 .
`Ong et al . , Double - Layer Capapcitance in Dual Lithium Ion Inser
`tion Cell . J Electrochem Soc . 1999 ; 146 : 4360-65 .
`Padhi et al . , Phospho - olivines as Positive - Electrod Materials for
`Rechargeable Lithium Batteries . J Electrochem Soc . 1997 ; 144 ( 4 ) : 1188
`94 .
`Pals et al . , Thermal Modeling of the Lithium Polymer Battery . I.
`Discharge Behavior of a Single Cell . J Electrochem Soc . 1995 ; 142 : 3274
`81 .
`Pals et al . , Thermal Modeling of the Lithium / Polymer Battery . II .
`Temperature Profiles in a Cell Stack . J Electrochem Soc . 1995 ; 142 : 3282
`88 .
`Pierson , Chapter 6. Virteous Carbon . Handbook of Carbon , Graph
`ite , Diamond and Fullerenes - Properties , Processing and Applica
`tions . 1993 ; 122-40 .
`Plitz et al . , Structure and Electrochemistry of Carbon - Metal Fluo
`ride Nanocomposites Fabricated by a Solid State Redox Conversion
`Reaction . J. Electrochem . Soc . 2005. 152 ( 2 ) : A307-15 . doi : 10.1149 /
`1.1842035 .
`Ravet et al . , Electroactivity of natural and synthetic triphylite . J
`Power Sci . 2001 ; 97-98 : 503-07 .
`Ravet et al . , Improved Iron Based Cathode Material . Abstract No.
`2014. 127 .
`Reed et al . , Introduction to the Principles of Ceramic Processing . J
`Wiley & Sons , New York . 1988 : 86-89 .
`Sander , Jonathan Samuel , " Scalable method for channeled low
`tortuous porosity in battery electrodes , ” Available online at : http : //
`p3.snf.ch/Project-148768 . Believed to have been made available on
`Jul . 7 , 2013 .
`Sander , Jonathan Samuel , “ Scalable method for channeled low
`tortuous porosity in battery electrodes , ” Available online at : http : //
`p3.snf.ch/Project-154584 . Believed to have been made available on
`Jul . 1 , 2014 .
`Sander et al . , High - performance battery electrodes via magnetic
`templating . Nature Energy . Jul . 11 , 2016 ; 1 : 16099 .
`Sander et al . , Magnetic Transport , Mixing and Release of Cargo
`with Tailored Nanoliter Droplets . Advanced Mater . May 15 ,
`2012 ; 24 ( 19 ) : 2582-7 .
`Soon et al . , Assembling unidirectionally frozen alumina / camphene
`bodies for aligned porous alumina ceramics with larger dimensions .
`Journal of European Ceramic Society . 2011 ; 31 : 415-9 .
`Tarascon et al . , Issues and challenges facing rechargeable lithium
`batteries . Nature . Nov. 15 , 2001 ; 414 ( 6861 ) : 359-67 .
`Thorat et al . , Quantifying tortuosity in porous Li - ion battery mate
`rials . Journal of Power Sources . 2009 ; 3 ( 15 ) : 1-9 .
`Tukamoto et al . , Electronic Conductivity of LiCoO2 and its Enhance
`ment by Magnesium Doping . J Electrochem Soc . 1997 ; 144 ( 9 ) : 3164
`68 .
`Vaccaro et al . , Electrochemical Investigations of Alkai - Metal Inter
`calation Reactions in TiSz : Chronoamperometric Determination of
`Mass and Charge Transport Properties of Liquid Electrolyte Sys
`tems . J Electrochem Soc . 1982 ; 129 : 682-88 .
`Van Oss , C.J. et al . , “ Applications of Net Repulsive Van Der Waals
`Forces Between Different Particles , Macromolecules or Biological
`Cells in Liquids , ” Colloids and Surfaces 1 : 45-56 ( 1980 ) .
`Van Oss , C.J. et al . , “ Comparison Between Antigen - Antibody
`Binding Energies and Interfacial Free Energies , ” Immunological
`Communications 6 ( 4 ) : 341-54 ( 1977 ) .
`Van Oss , C.J. et al . , “ Repulsive Van Der Waals Forces . I. Complete
`Dissociation of Antigen - Antibody Complexes by Means of Nega
`tive Van Der Waals Forces , ” Immunological Communications 8 ( 1 ) : 11
`29 ( 1979 ) .
`
`LUMENIS EX1009
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`US 10,675,819 B2
`Page 6
`
`( 56 )
`
`References Cited
`OTHER PUBLICATIONS
`Van Oss , C.J. et al . , “ Repulsive Van Der Waals Forces . II Mecha
`nism of Hydrophobic Chromatography , " Separation Science and
`Technology 14 ( 4 ) : 305-17 ( 1979 ) .
`Vijayaraghavan et al . , An analytical method to determine tortuosity
`in rechargeable battery electrodes . J Electrochemical Society .
`2012 ; 159 ( 5 ) : A548-552 .
`Wang , C. et al . , “ All Solid - State Li / Li MnO , Polymer Battery Using
`Ceramic Modified Polymer Electrolytes , ” J. Electrochemical Soc .
`149 ( 8 ) : A967-72 ( 2002 ) .
`Yamada et al . , Crystal Chemistry of the Olivine - Type Li ( MnyFel
`y ) PO4 and ( MNyFel - y ) PO4 as Possible 4 V Cathode Materials for
`Lithium Batteries . J Electrochem Soc . 2001 ; 148 ( 8 ) : A960-67 .
`Yamada et al . , Optimized LiFePO4 for Lithium Battery Cathodes .
`J Electrochem Soc . 2001 ; 148 ( 3 ) : A224-29 .
`Zacharias et al . , Direct measurements of effective ionic transport in
`porous Li - ion electrodes . Journal of Electrochemical Society .
`2013 ; 160 ( 2 ) : A306 - A311 .
`Zallen et al . , 4.7 . Continuum Percolation and the Critical Volume
`Fraction . The Physics of Amorphous Solids . J Wiley & Sons , NY .
`1983 : 183-91 .
`International Preliminary Report on Patentability for PCT / US2015 /
`053761 , dated Apr. 13 , 2017 .
`Mawdsley et al . , Fracture behavior of alumina / monazite multilayer
`laminates . J Am Ceram Soc . 2000 ; 83 ( 4 ) : 802-8 .
`Van Hoy et al . , Microfabrication of ceramics by co - extrusion . J Am
`Ceram Soc . Jan. 1998 ; 81 ( 1 ) : 152-8 .
`* cited by examiner
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`U.S. Patent
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`Sheet 1 of 18
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`US 10,675,819 B2
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`100
`
`102
`
`104
`
`100
`
`102
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`
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`112
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`
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`
`106
`
`FIG . IC
`
`FIG . ID
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`Sheet 2 of 18
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`US 10,675,819 B2
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`matrix
`200
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`droplets
`202
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`
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`U.S. Patent
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`Jun . 9 , 2020
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`Sheet 3 of 18
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`US 10,675,819 B2
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`a Ferrofluid emulsion droplet
`
`.
`
`.
`
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`Solvent Electrode particle
`FIG . 3A
`
`Solvent evaporation
`C
`Continuous phase evaporates first
`Then dispersed phased
`
`d
`
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`
`Consolidation
`
`FIG . 3C
`
`FIG . 3D
`
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`Sheet 4 of 18
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`US 10,675,819 B2
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`
`
`Matrix consolidation
`
`
`
`Solvent evaporation
`
`
`
`Matrix consolidation
`
`
`
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`
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`
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`
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`Sheet 5 of 18
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`FIG . 5A
`
`FIG . 5B
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`Sheet 6 of 18
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`Potential vs Lii ( V )
`3.5
`
`3.0
`
`25
`
`120
`
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`Capacity ( mAh )
`
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`
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`
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`Areal Capacity ( mAh cm )
`FIG . 5C
`
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`
`mi
`
`FIG . 5D
`
`LUMENIS EX1009
`Pa