Journal of Electroanalytical Chemistry 837 (2019) 151-158
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`Contents lists available at ScienceDirect
` !"#$"#% &’%#% ()(’&(*&$ (# +,’$",$-’.$,#
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`Journal of Electroanalytical Chemistry
`/!0."(& !1 2&$,#.!("(&3#’,(& 4$5’%#.3
`
`1 . Electra analytical
`Chemistry
`
`ELSEVI ER
`
`journal homepage: www.elsevier.com/locate/jelechem
` !"#$%& ’!()*%+), ---.)&/)01)#.2!(3&!2%4)3 )&)2’)(
`
`Laminated Lithium Ion Batteries with improved fast charging capability
`6(5’"(#$7 6’#4’05 8!" 9(##$.’$% :’#4 ’5;.!)$7 1(%# ,4(.<’"< ,(;(*’&’#3
`
`=(.#’" >.("?$"*$.<$.(@ @ =(74() +’"<4(@ A&$B("7$. -’"#$.(@ +$*(%#’(" /("?!:?%3(@
`Martin Frankenberger' Madhav Singh', Alexander Dintera, Sebastian Jankowksy',
`A&$B("7$. +,45’7#*@ C(.&DE$’"F G$##’"<$.(
`Alexander Schmide, Karl-Heinz Pettingera
`Versity of Applied Sciences Lanclshu4 Technology Center for Energy, Wiesenweg I, 94099 Ruhstorf, Germany
`( !"#$%&"’( )* +,,-"$. /0"$!0$& 12!.&34’5 6$03!)-)7( 8$!’$% *)% 9!$%7(5 :"$&$!;$7 <5 =>?== @43&’)%*5 A$%B2!(
`'Karlsruhe Institute of Technology (R7T), Institute for Applied Materials-Energy Storage Systems (IAM-ESS), 76344
`enstetn-Leopvldshoftn, Germany
`* C2%-&%43$ D!&’"’4’$ )* 6$03!)-)7( ECD6F5 D!&’"’4’$ *)% +,,-"$. G2’$%"2-&H9!$%7( /’)%27$ /(&’$B& ED+GH9//F5 IJK>> 977$!&’$"!H1$),)-.&32*$!5 A$%B2!(
`
`ARTICLE INFO
`A H I 8 6 2 8 J > K
`
`ABSTRACT
`A 9 + I H A I
`
`Keywords:
`C$(;)%.&L
`Lithium-ion battery
`6’#4’05D’!" *(##$.3
`Lamination
`6(5’"(#’!"
`Fast charging capability
`>(%# ,4(.<’"< ,(;(*’&’#3
`Fast discharge capability
`>(%# 7’%,4(.<$ ,(;(*’&’#3
`Cell ccoarresston
` $&& ,!5;.$%%’!"
`Enhanced cycling stability
`2"4(",$7 ,3,&’"< %#(*’&’#3
`
`The fast charge and discharge capability of lithium-ion batteries is improved by applying a lamination step
`I4$ 1(%# ,4(.<$ ("7 7’%,4(.<$ ,(;(*’&’#3 !1 &’#4’05D’!" *(##$.’$% ’% ’5;.!)$7 *3 (;;&3’"< ( &(5’"(#’!" %#$;
`during cell assembly. Electrode sheets and separator are laminated into one stack which improves the electro-
`70.’"< ,$&& (%%$5*&3L 2&$,#.!7$ %4$$#% ("7 %$;(.(#!. (.$ &(5’"(#$7 ’"#! !"$ %#(,? :4’,4 ’5;.!)$% #4$ $&$,#.!D
`chemical performance as well as the stack assembly process. The effect of non-laminated and laminated inter-
`,4$5’,(& ;$.1!.5(",$ (% :$&& (% #4$ %#(,? (%%$5*&3 ;.!,$%%L I4$ $M$,# !1 "!"D&(5’"(#$7 ("7 &(5’"(#$7 ’"#$.D
`faces on the reversible capacity during cycling axe studied thoroughly in half-cell and full-cell configurations.
`1(,$% !" #4$ .$)$.%’*&$ ,(;(,’#3 70.’"< ,3,&’"< (.$ %#07’$7 #4!.!0<4&3 ’" 4(&1D,$&& ("7 10&&D,$&& ,!"N<0.(#’!"%L
`The fully-laminated cells show a reduction in the capacity losses of 3%, 5% and 12% upon cycling at 2C, 3C and
`I4$ 10&&3D&(5’"(#$7 ,$&&% %4!: ( .$70,#’!" ’" #4$ ,(;(,’#3 &!%%$% !1 OP@ QP ("7 RSP 0;!" ,3,&’"< (# S @ O ("7
`5C-rate, respectively, while capacity losses of 6%, 11% and 23% axe observed in non-laminated cells at the same
`Q D.(#$@ .$%;$,#’)$&3@ :4’&$ ,(;(,’#3 &!%%$% !1 TP@ RRP ("7 SOP (.$ !*%$.)$7 ’" "!"D&(5’"(#$7 ,$&&% (# #4$ %(5$
`C-rates. A significant reduction in the capacity fading at high C-rates is observed upon lamination. Additional
` D.(#$%L A %’<"’N,("# .$70,#’!" ’" #4$ ,(;(,’#3 1(7’"< (# 4’<4 D.(#$% ’% !*%$.)$7 0;!" &(5’"(#’!"L A77’#’!"(&
`compression is applied on the cells to compare the effect of lamination and compression on the cell performance.
`,!5;.$%%’!" ’% (;;&’$7 !" #4$ ,$&&% #! ,!5;(.$ #4$ $M$,# !1 &(5’"(#’!" ("7 ,!5;.$%%’!" !" #4$ ,$&& ;$.1!.5(",$L
`The laminated cells show an improvement in the fast charging capability in cornparison to the non-laminated
`I4$ &(5’"(#$7 ,$&&% %4!: (" ’5;.!)$5$"# ’" #4$ 1(%# ,4(.<’"< ,(;(*’&’#3 ’" ,!5;(.’%!" #! #4$ "!"D&(5’"(#$7
`cells.
`,$&&%L
`
`1. Introduction
` ! "#$%&’()$*&#
`
`More than 40 years after production of the first commercial lithium
`=!.$ #4(" UV 3$(.% (1#$. ;.!70,#’!" !1 #4$ N.%# ,!55$.,’(& &’#4’05
`cell by Sanyo in 1970s, [-I ] the lithium-ion battery (LIB) technology has
`,$&& *3 +("3! ’" RWXV%@ YRZ #4$ &’#4’05D’!" *(##$.3 [689\ #$,4"!&!<3 4(%
`become a main contributor for the storage devices in the field of re-
`*$,!5$ ( 5(’" ,!"#.’*0#!. 1!. #4$ %#!.(<$ 7$)’,$% ’" #4$ N$&7 !1 .$D
`chargeable batteries. LIB technology needs further improvement in
`,4(.<$(*&$ *(##$.’$%L 689 #$,4"!&!<3 "$$7% 10.#4$. ’5;.!)$5$"# ’"
`terms of fast charging capability which can reduce the charging time
`#$.5% !1 1(%# ,4(.<’"< ,(;(*’&’#3 :4’,4 ,(" .$70,$ #4$ ,4(.<’"< #’5$
`from hours to minutes especially for the electric vehicle applications.
`1.!5 4!0.% #! 5’"0#$% $%;$,’(&&3 1!. #4$ $&$,#.’, )$4’,&$ (;;&’,(#’!"%L
`Enormous research is going on to improve the cell components such as
`2"!.5!0% .$%$(.,4 ’% <!’"< !" #! ’5;.!)$ #4$ ,$&& ,!5;!"$"#% %0,4 (%
`active materials, [2,A electrolyte, [4] separator [5,,.5] and manu-
`(,#’)$ 5(#$.’(&%@ YS@OZ $&$,#.!&3#$@ YUZ %$;(.(#!. YQ@TZ ("7 5("0D
`facturing steps [7] in order to increase the energy density, power
`1(,#0.’"< %#$;% YXZ ’" !.7$. #! ’",.$(%$ #4$ $"$.<3 7$"%’#3@ ;!:$.
`density, lifetime and reduce the cost. The performance of lithium-ion
`7$"%’#3@ &’1$#’5$ ("7 .$70,$ #4$ ,!%#L I4$ ;$.1!.5(",$ !1 &’#4’05D’!"
`battery electrodes has been improved by varying the thickness [f1,9]
`*(##$.3 $&$,#.!7$% 4(% *$$" ’5;.!)$7 *3 )(.3’"< #4$ #4’,?"$%% Y]@WZ
`and porosity of the electrodes [-I 0], controlling the stack pressure
`("7 ;!.!%’#3 !1 #4$ $&$,#.!7$% YRVZ@ ,!"#.!&&’"< #4$ %#(,? ;.$%%0.$
`[11-15] and tuning the lithium ion diffusion paths in electrodes via
`YRR^RQZ ("7 #0"’"< #4$ &’#4’05 ’!" 7’M0%’!" ;(#4% ’" $&$,#.!7$% )’(
`modified manufacturing processes, for example by controlling the
`5!7’N$7 5("01(,#0.’"< ;.!,$%%$%@ 1!. $B(5;&$ *3 ,!"#.!&&’"< #4$
`graphite particle orientation normal to the current collector surface
`<.(;4’#$ ;(.#’,&$ !.’$"#(#’!" "!.5(& #! #4$ ,0..$"# ,!&&$,#!. %0.1(,$
`during the coating step using a magnetic field, [1
`or via laser struc-
`70.’"< #4$ ,!(#’"< %#$; 0%’"< ( 5(<"$#’, N$&7@ YRTZ !. )’( &(%$. %#.0,D
`turing of graphite anodes, silicon/graphite anodes, NMC cathodes or
`#0.’"< !1 <.(;4’#$ ("!7$%@ %’&’,!"_<.(;4’#$ ("!7$%@ J= ,(#4!7$% !.
`IiMn204 cathodes []7-2'0'].
`6’="SKU ,(#4!7$% YRX^SVZL
`The laser structuring creates additional lithium ion diffusion path-
`I4$ &(%$. %#.0,#0.’"< ,.$(#$% (77’#’!"(& &’#4’05 ’!" 7’M0%’!" ;(#4D
`ways and increases the active surface area of thick NMC and graphite
`:(3% ("7 ’",.$(%$% #4$ (,#’)$ %0.1(,$ (.$( !1 #4’,? J= ("7 <.(;4’#$
`electrodes, thus enhances the discharge capacities at higher C-rates
`$&$,#.!7$%@ #40% $"4(",$% #4$ 7’%,4(.<$ ,(;(,’#’$% (# 4’<4$. D.(#$%
`[-1 7,-1 9] . Besides, LIB cycling stability and aging mechanism can also be
`YRX@RWZL 9$%’7$%@ 689 ,3,&’"< %#(*’&’#3 ("7 (<’"< 5$,4("’%5 ,(" (&%! *$
`
`improved by varying the stack pressure, [ I I - 1 5] which influences the
`’5;.!)$7 *3 )(.3’"< #4$ %#(,? ;.$%%0.$@ YRR^RQZ :4’,4 ’"‘0$",$% #4$
`distribution of solid electrolyte interface (SEI) or plated lithium de-
`7’%#.’*0#’!" !1 %!&’7 $&$,#.!&3#$ ’"#$.1(,$ [+28\ !. ;&(#$7 &’#4’05 7$D
`position on the graphite-separator interface [12,12,21]. It has been
`;!%’#’!" !" #4$ <.(;4’#$D%$;(.(#!. ’"#$.1(,$ YRS@RO@SRZL 8# 4(% *$$"
`reported that the high stack pressure causes the higher capacity fade, so
`.$;!.#$7 #4(# #4$ 4’<4 %#(,? ;.$%%0.$ ,(0%$% #4$ 4’<4$. ,(;(,’#3 1(7$@ %!
`lower stack pressure is required to extend the life time. In addition, the
`&!:$. %#(,? ;.$%%0.$ ’% .$a0’.$7 #! $B#$"7 #4$ &’1$ #’5$L 8" (77’#’!"@ #4$
`non-uniform surface of the electrodes also induces non-uniform pres-
`"!"D0"’1!.5 %0.1(,$ !1 #4$ $&$,#.!7$% (&%! ’"70,$% "!"D0"’1!.5 ;.$%D
`sure at the interfaces among different electrode layers and the ampli-
`%0.$ (# #4$ ’"#$.1(,$% (5!"< 7’M$.$"# $&$,#.!7$ &(3$.% ("7 #4$ (5;&’D
`tude of the pressure varies during charging and discharging [I ll
`#07$ !1 #4$ ;.$%%0.$ )(.’$% 70.’"< ,4(.<’"< ("7 7’%,4(.<’"< YRRZL
`Non-uniform space among the electrodes and separator results in
`J!"D0"’1!.5 %;(,$ (5!"< #4$ $&$,#.!7$% ("7 %$;(.(#!. .$%0&#% ’"
`longer diffusion paths at the interfaces in the cell stacks, as shown in
`&!"<$. 7’M0%’!" ;(#4% (# #4$ ’"#$.1(,$% ’" #4$ ,$&& %#(,?%@ (% %4!:" ’"
`schematic rig, i a. In this regard, lamination technique stabilizes the
`%,4$5(#’, >’<L R(L 8" #4’% .$<(.7@ &(5’"(#’!" #$,4"’a0$ %#(*’&’F$% #4$
`electrode-separator interfaces, which shortens the lithium diffusion
`$&$,#.!7$D%$;(.(#!. ’"#$.1(,$%@ :4’,4 %4!.#$"% #4$ &’#4’05 7’M0%’!"
`paths at the interfaces as well as stabilizing the active surface area of
`;(#4% (# #4$ ’"#$.1(,$% (% :$&& (% %#(*’&’F’"< #4$ (,#’)$ %0.1(,$ (.$( !1
`I b), and thus homo-
`the electrodes during cycling significantly (Fig,.
`#4$ $&$,#.!7$% 70.’"< ,3,&’"< %’<"’N,("#&3 [>’<L R*\@ ("7 #40% 4!5!D
`genize the liquid phase concentration [17] of the lithium ions on the
`<$"’F$ #4$ &’a0’7 ;4(%$ ,!",$"#.(#’!" YRXZ !1 #4$ &’#4’05 ’!"% !" #4$
`active material particle surface. The lamination technique provides the
`(,#’)$ 5(#$.’(& ;(.#’,&$ %0.1(,$L I4$ &(5’"(#’!" #$,4"’a0$ ;.!)’7$% #4$
`slight mobilization of the polymer binder chains both in the separator
`%&’<4# 5!*’&’F(#’!" !1 #4$ ;!&35$. *’"7$. ,4(’"% *!#4 ’" #4$ %$;(.(#!.
`and electrode by applying heat and pressure which interlinks the
`("7 $&$,#.!7$ *3 (;;&3’"< 4$(# ("7 ;.$%%0.$ :4’,4 ’"#$.&’"?% #4$
`electrode-separator interfaces and also maintains the surface porosity of
`$&$,#.!7$D%$;(.(#!. ’"#$.1(,$% ("7 (&%! 5(’"#(’"% #4$ %0.1(,$ ;!.!%’#3 !1
`the electrode and the separator. The necessity for mobilization of
`#4$ $&$,#.!7$ ("7 #4$ %$;(.(#!.L I4$ "$,$%%’#3 1!. 5!*’&’F(#’!" !1
`polymer binder chains in all components limits the choice of binder to
`;!&35$. *’"7$. ,4(’"% ’" (&& ,!5;!"$"#% &’5’#% #4$ ,4!’,$ !1 *’"7$. #!
`thermoplastic polymers with similar melting points. Heat-induced
`#4$.5!;&(%#’, ;!&35$.% :’#4 %’5’&(. 5$&#’"< ;!’"#%L E$(#D’"70,$7
`polymer chain mobilization must not exceed the melting temperature of
`;!&35$. ,4(’" 5!*’&’F(#’!" 50%# "!# $B,$$7 #4$ 5$&#’"< #$5;$.(#0.$ !1
`the polymer in order to prevent the production of a nonporous interface
`#4$ ;!&35$. ’" !.7$. #! ;.$)$"# #4$ ;.!70,#’!" !1 ( "!";!.!0% ’"#$.1(,$
`
`Corresponding author.
` !..$%;!"7’"< (0#4!.L
`E-mail address: martin-frankenberger@myturn.de
`Frankenberger).
`9HB2"- 2..%$&&L 5(.#’"D1.("?$"*$.<$.e53#05L7$ [=L >.("?$"*$.<$.\L
`
`hup6://ali.org/10.1016/j jp,lech ern, 2' 019.02.030
`4##;%b__7!’L!.<_RVLRVRT_cLc$&$,4$5LSVRWLVSLVOV
`Received 19 September 2018; Received in revised form 29 January 2019; Accepted 15 February 2019
`H$,$’)$7 RW +$;#$5*$. SVR]d H$,$’)$7 ’" .$)’%$7 1!.5 SW /("0(.3 SVRWd A,,$;#$7 RQ >$*.0(.3 SVRW
`Available online 17 February 2019
`2K:BC:;C>"FECBE>")/"6>;GJ:GL"*()1
`1572-6657/ © 2019 Elsevier B.V. All rights reserved.
`)-/*%..-/’"M"*()1"5CH>KB>G"3&9&"2CC"GB@AIH"G>H>GK>=&
`
`JLab/Cambridge, Exh. 1030, p. 1
`
`

`

`Frankenbager, a al
`GN P%2!W$![$%7$%5 $’ 2-N
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`(a)
`
`Separator
`
`• — —
`
`•
`
`.
`
`
`
`• NMC
`
`Carbon Black
`4.10 Graphite
`
`(b)
`
`4
`
`14
`
`r. , •
`
`J0w7td of gatroanalytical Climb:try 837 (2019) 151-158
`/9=:806"93".621<:90806><5106"-4275;<:>"+(*"#’%&,$"&)&?&)+
`
`Fig. 1. Schematics of electrode-separator
`3*4! ! +,4$5(#’,% !1 $&$,#.!7$D%$;(.(#!.
`lamination technique (a) non-laminated
`&(5’"(#’!" #$,4"’a0$d
`[(\ "!"D&(5’"(#$7
`single cell stack (b) laminated single cell
`%’"<&$ ,$&& %#(,? [*\ &(5’"(#$7 %’"<&$ ,$&&
`stack.
`%#(,?L
`
`block.
`*&!,?L
`Lamination technique has been well known for some decades
`6(5’"(#’!" #$,4"’a0$ 4(% *$$" :$&& ?"!:" 1!. %!5$ 7$,(7$%
`[22,2A for the stacking process simplification which reduces the de-
`YSS@SOZ 1!. #4$ %#(,?’"< ;.!,$%% %’5;&’N,(#’!" :4’,4 .$70,$% #4$ 7$D
`fects occurring due to electrode misplacement at the anode-separator-
`1$,#% !,,0..’"< 70$ #! $&$,#.!7$ 5’%;&(,$5$"# (# #4$ ("!7$D%$;(.(#!.D
`cathode compound [21. Lamination technology connects the inter-
`,(#4!7$ ,!5;!0"7 YSUZL 6(5’"(#’!" #$,4"!&!<3 ,!""$,#% #4$ ’"#$.D
`layers, separator-cathode and separator-anode, physically by using a
`&(3$.%@ %$;(.(#!.D,(#4!7$ ("7 %$;(.(#!.D("!7$@ ;43%’,(&&3 *3 0%’"< (
`roller lamination machine and therefore, maximizes the physical and
`.!&&$. &(5’"(#’!" 5(,4’"$ ("7 #4$.$1!.$@ 5(B’5’F$% #4$ ;43%’,(& ("7
`ionic contacts as well as minimizing the voids at the interfaces (174g, ).
`’!"’, ,!"#(,#% (% :$&& (% 5’"’5’F’"< #4$ )!’7% (# #4$ ’"#$.1(,$% [>’<L R\L
`First time, the lamination technology was used in the assembly
`>’.%# #’5$@ #4$ &(5’"(#’!" #$,4"!&!<3 :(% 0%$7 ’" #4$ (%%$5*&3
`process during the lithium ion battery production in 1996 [22]. Later
`;.!,$%% 70.’"< #4$ &’#4’05 ’!" *(##$.3 ;.!70,#’!" ’" RWWT YSSZL 6(#$.
`specific roller lamination technique was reported as a binding tech-
`%;$,’N, .!&&$. &(5’"(#’!" #$,4"’a0$ :(% .$;!.#$7 (% ( *’"7’"< #$,4D
`nique to prevent the air bubbles and wrinkles within the laminated
`"’a0$ #! ;.$)$"# #4$ (’. *0**&$% ("7 :.’"?&$% :’#4’" #4$ &(5’"(#$7
`material for preparing the supercapacitor electrode on a current col-
`5(#$.’(& 1!. ;.$;(.’"< #4$ %0;$.,(;(,’#!. $&$,#.!7$ !" ( ,0..$"# ,!&D
`lector [2-5]. Winding and lamination technologies are typically used as
`&$,#!. YSQZL f’"7’"< ("7 &(5’"(#’!" #$,4"!&!<’$% (.$ #3;’,(&&3 0%$7 (%
`state-of-the-art technologies in industrial LIB production lines.
`%#(#$D!1D#4$D(.# #$,4"!&!<’$% ’" ’"70%#.’(& 689 ;.!70,#’!" &’"$%L
`The lamination technique is a simple and easy-to-apply technology,
`I4$ &(5’"(#’!" #$,4"’a0$ ’% ( %’5;&$ ("7 $(%3D#!D(;;&3 #$,4"!&!<3@
`which simplifies the stacking process by reducing the number of com-
`:4’,4 %’5;&’N$% #4$ %#(,?’"< ;.!,$%% *3 .$70,’"< #4$ "05*$. !1 ,!5D
`ponents. The lamination process enables fast assembly speeds up to
`;!"$"#%L I4$ &(5’"(#’!" ;.!,$%% $"(*&$% 1(%# (%%$5*&3 %;$$7% 0; #!
`100 mimin and therefore lowers the costs of the assembly process.
`RVV 5_5’" ("7 #4$.$1!.$ &!:$.% #4$ ,!%#% !1 #4$ (%%$5*&3 ;.!,$%%L
`Besides, the lamination technique improves the electrochemical per-
`9$%’7$%@ #4$ &(5’"(#’!" #$,4"’a0$ ’5;.!)$% #4$ $&$,#.!,4$5’,(& ;$.D
`formance of the cell, in terms of improving cycling stability, reducing
`1!.5(",$ !1 #4$ ,$&&@ ’" #$.5% !1 ’5;.!)’"< ,3,&’"< %#(*’&’#3@ .$70,’"<
`aging effects and stabilizing cell performance even in case of vacuum
`(<’"< $M$,#% ("7 %#(*’&’F’"< ,$&& ;$.1!.5(",$ $)$" ’" ,(%$ !1 )(,005
`reduction in the cell, in comparison to the above mentioned additional
`.$70,#’!" ’" #4$ ,$&&@ ’" ,!5;(.’%!" #! #4$ (*!)$ 5$"#’!"$7 (77’#’!"(&
`electrode modification technologies.
`$&$,#.!7$ 5!7’N,(#’!" #$,4"!&!<’$%L
`In this article, we present a detailed study of the electrode-separator
`8" #4’% (.#’,&$@ :$ ;.$%$"# ( 7$#(’&$7 %#073 !1 #4$ $&$,#.!7$D%$;(.(#!.
`lamination in full cell configuration at higher C-rates. This study will
`&(5’"(#’!" ’" 10&& ,$&& ,!"N<0.(#’!" (# 4’<4$. D.(#$%L I4’% %#073 :’&&
`reveal the significant improvement in the fast charging and discharging
`.$)$(& #4$ %’<"’N,("# ’5;.!)$5$"# ’" #4$ 1(%# ,4(.<’"< ("7 7’%,4(.<’"<
`capability of single cells after applying the lamination technique.
`,(;(*’&’#3 !1 %’"<&$ ,$&&% (1#$. (;;&3’"< #4$ &(5’"(#’!" #$,4"’a0$L
`
`2. Experimental
`+! ,-./%*0/#$12
`
`2.1. Materials
`MN<N G2’$%"2-&
`
`Commercially available battery grade cathode material LiNiv3Mnii
` !55$.,’(&&3 ()(’&(*&$ *(##$.3 <.(7$ ,(#4!7$ 5(#$.’(& 6’J’R_O="R_
`3Cows0 2 (NM-3102 h, BASF, Germany - former TODA AMERICA, USA)
`O !R_OKS [J=DORVS 4@ O+/P5 g$.5("3 ^ 1!.5$. 6QR+ +G9@D8+5 h+A\
`and anode material graphite (MAGE3, HITACHI CHEMICAL, Japan)
`("7 ("!7$ 5(#$.’(& <.(;4’#$ [=Ag2O@ SD6+8SD 8S9GD8+1@ /(;("\
`were used as active materials. Conductive carbon (Super C65, IMERYS,
`:$.$ 0%$7 (% (,#’)$ 5(#$.’(&%L !"70,#’)$ ,(.*!" [+0;$. TQ@ DG9@T/5
`Switzerland - former TDICAL, Switzerland), cathode conductive gra-
`+:’#F$.&("7 ^ 1!.5$. 6DG8+1@ +:’#F$.&("7\@ ,(#4!7$ ,!"70,#’)$ <.(D
`phite (ICS6L, MIRES) and anode conductive graphite (SFG6L, MERYS)
`;4’#$ [C+T6@ DG9@T/\ ("7 ("!7$ ,!"70,#’)$ <.(;4’#$ [+>gT6@ DG9@T/\
`were used as conductive additives. PVDF (Solefa 5130, SOLVAY, Italy)
`:$.$ 0%$7 (% ,!"70,#’)$ (77’#’)$%L Gi-> [+!&$1" QROV@ /Q1U+T@ 8#(&3\
`was used as binder. N-methyl-pyrrolidone (Overlock, Germany) was
`:(% 0%$7 (% *’"7$.L VD5$#43&D;3..!&’7!"$ [Q#$%-20W@ g$.5("3\ :(%
`used as solvent. 1 M LiPF6 - ethylene carbonate (EC): ethylmethylcar-
`0%$7 (% %!&)$"#L R = 6’G>T D $#43&$"$ ,(.*!"(#$ [2 \b $#43&5$#43&,(.D
`bonate (EMC) 3:7 w/w (Selectilyte LP57, BASF, Germany) and vinylene
`*!"(#$ [2= \ ObX ;_: [+$&$,#’&3#$ 6GQX@ O+/P@ g$.5("3\ ("7 )’"3&$"$
`carbonate (Vinylene Carbonate F, BASF, Germany) were used as elec-
`,(.*!"(#$ [i’"3&$"$ (.*!"(#$ 2@ O+/P@ g$.5("3\ :$.$ 0%$7 (% $&$,D
`trolyte. A laminate type aluminum pouch film (SHOWA DENKO
`#.!&3#$L A &(5’"(#$ #3;$ (&05’"05 ;!0,4 N&5 [/SQ:+ R9VCQ
`AMERICA, USA) was used as housing of pouch cells. Pure lithium and
`+G9@D8+@ h+A\ :(% 0%$7 (% 4!0%’"< !1 ;!0,4 ,$&&%L G0.$ &’#4’05 ("7
`glass microfibre filter (Glass Fibre Filter Grade 691, VWR-avantor, USA)
`<&(%% 5’,.!N*.$ N&#$. [g&(%% >’*.$ >’&#$. g.(7$ TWR@ U:@H2#2!’)%@ h+A\
`were used for T-cells (half-cell). A self-standing inorganic filled (Al2O5)
`:$.$ 0%$7 1!. ID,$&&% [4(&1D,$&&\L A %$&1D%#("7’"< ’"!.<("’, N&&$7 [A&SKO\
`separator film with a PVDF/HFP Copolymer as binding agent, was used
`%$;(.(#!. N&5 :’#4 ( Gi->_E>G !;!&35$. (% *’"7’"< (<$"#@ :(% 0%$7
`for the pouch cell (full-cell) configuration. All materials and substrates
`1!. #4$ ;!0,4 ,$&& [10&&D,$&&\ ,!"N<0.(#’!"L A&& 5(#$.’(&% ("7 %0*%#.(#$%
`were used as received.
`:$.$ 0%$7 (% .$,$’)$7L
`
`by mixing MAGE3 graphite (90 wt%), PVDF (7 wt%), Super C65 carbon
`*3 5’B’"< =Ag2O <.(;4’#$ [WV :#P\@ Gi-> [X :#P\@ +0;$. TQ ,(.*!"
`(2 wt%) and SFG6L graphite (1 wt%) with NMP to give a final solid
`[S :#P\ ("7 +>gT6 <.(;4’#$ [R :#P\ :’#4 J=G #! <’)$ ( N"(& %!&’7
`content of 50 wt%. The electrode slurries were prepared in a planetary
`,!"#$"# !1 QV :#PL I4$ $&$,#.!7$ %&0..’$% :$.$ ;.$;(.$7 ’" ( ;&("$#(.3
`mixer (DC-2, INOUE, Japan) and were single-side coated by a doctor-
`5’B$. [IjDS@ 8JKh2@ /(;("\ ("7 :$.$ %’"<&$D%’7$ ,!(#$7 *3 ( 7!,#!.D
`blade water in a roll-to-roll process coating machine. Electrodes were
`*&(7$ ,!(#$. ’" ( .!&&D#!D.!&& ;.!,$%% ,!(#’"< 5(,4’"$L 2&$,#.!7$% :$.$
`dried in-line in a two-step drying tunnel at the temperature range of
`7.’$7 ’"D&’"$ ’" ( #:!D%#$; 7.3’"< #0""$& (# #4$ #$5;$.(#0.$ .("<$ !1
`135-150 'C. Low electrode mass loadings were chosen to act as high
`ROQ^RQV k L 6!: $&$,#.!7$ 5(%% &!(7’"<% :$.$ ,4!%$" #! (,# (% 4’<4
`capacity and high power reference system [2,A. The averaged active
`,(;(,’#3 ("7 4’<4 ;!:$. .$1$.$",$ %3%#$5 YSTZL I4$ ()$.(<$7 (,#’)$
`mass loadings of cathode and anode electrodes were —6.9 mg-cm -2
`5(%% &!(7’"<% !1 ,(#4!7$ ("7 ("!7$ $&$,#.!7$% :$.$ lTLW 5<m,5nS
`(1.13 mAh-cm-2) and —3.4 mgcm —2 (1.28 mAh-cm- 2), respectively.
`[RLRO 5A4m,5nS\ ("7 lOLU 5<m,5nS [RLS] 5A4o,5nS\@ .$%;$,#’)$&3L
`The cathode and anode capacity balancing factor was 1:1.14 in the full
`I4$ ,(#4!7$ ("7 ("!7$ ,(;(,’#3 *(&(",’"< 1(,#!. :(% RbRLRU ’" #4$ 10&&
`cells. The electrodes in full cell configuration have mass in the range of
`,$&&%L I4$ $&$,#.!7$% ’" 10&& ,$&& ,!"N<0.(#’!" 4()$ 5(%% ’" #4$ .("<$ !1
`0.245-0.278 g of NMC and capacity in the range of 0.041-0.047 Ah.
`VLSUQ^VLSX] < !1 J= ("7 ,(;(,’#3 ’" #4$ .("<$ !1 VLVUR^VLVUX A4L
`
`2.3. Cell preparation
`MNKN 8$-- ,%$,2%2’")!
`
`The active areas of cathode and anode sheets were 5 x 8 cm2 and
`I4$ (,#’)$ (.$(% !1 ,(#4!7$ ("7 ("!7$ %4$$#% :$.$ Q p ] ,5S ("7
`5.4 x 8.4 cm2 within the pouch cell. Cathode, anode and separator
`QLU p ]LU ,5S :’#4’" #4$ ;!0,4 ,$&&L (#4!7$@ ("!7$ ("7 %$;(.(#!.
`were laminated to make a single stack by using a lamination machine
`:$.$ &(5’"(#$7 #! 5(?$ ( %’"<&$ %#(,? *3 0%’"< ( &(5’"(#’!" 5(,4’"$
`(BLE 282 D, MANZ ltnly - former ARCOTRONICS laxlia S.p.A., Italy) at
`[962 S]S -@ G+VY D’2-( ^ 1!.5$. +@8Q6@QVD8/ D’2-"2 /N,N+N@ 8#(&3\ (#
`the roll speed of 138 nymin-1, using a line force of 157 N-cm-1 in the
`#4$ .!&& %;$$7 !1 RLO] 5m5’"nR@ 0%’"< ( &’"$ 1!.,$ !1 RQX Jm,5nR ’" #4$
`temperature range 100-120 C.
`#$5;$.(#0.$ .("<$ RVV^RSV k L
`To analyze the effect of lamination on the electrochemical perfor-
`I! ("(&3F$ #4$ $M$,# !1 &(5’"(#’!" !" #4$ $&$,#.!,4$5’,(& ;$.1!.D
`mance of cathode and anode individually, cathode-separator stacks
`5(",$ !1 ,(#4!7$ ("7 ("!7$ ’"7’)’70(&&3@ ,(#4!7$D%$;(.(#!. %#(,?%
`were laminated by laminating a copper-separator-cathode stack, later
`:$.$ &(5’"(#$7 *3 &(5’"(#’"< ( ,!;;$.D%$;(.(#!.D,(#4!7$ %#(,?@ &(#$.
`the copper was replaced with the appropriate anode without any fur-
`#4$ ,!;;$. :(% .$;&(,$7 :’#4 #4$ (;;.!;.’(#$ ("!7$ :’#4!0# ("3 10.D
`ther lamination. Similarly, anode-separator stacks were laminated by
`#4$. &(5’"(#’!"L +’5’&(.&3@ ("!7$D%$;(.(#!. %#(,?% :$.$ &(5’"(#$7 *3
`laminating an aluminum-separator-anode stack, later the aluminum foil
`&(5’"(#’"< (" (&05’"05D%$;(.(#!.D("!7$ %#(,?@ &(#$. #4$ (&05’"05 1!’&
`was removed from the stack, and replaced with the appropriate cathode
`:(% .$5!)$7 1.!5 #4$ %#(,?@ ("7 .$;&(,$7 :’#4 #4$ (;;.!;.’(#$ ,(#4!7$
`without any further lamination. Nickel and aluminum tabs were welded
`:’#4!0# ("3 10.#4$. &(5’"(#’!"L J’,?$& ("7 (&05’"05 #(*% :$.$ :$&7$7
`onto the anode and cathode electrodes by ultrasonic welding. Pre-as-
`!"#! #4$ ("!7$ ("7 ,(#4!7$ $&$,#.!7$% *3 0&#.(%!"’, :$&7’"<L G.$D(%D
`sembled pouch cell stacks were dried at 110 'V for 12 h under vacuum.
`%$5*&$7 ;!0,4 ,$&& %#(,?% :$.$ 7.’$7 (# RRV k 1!. RS 4 0"7$. )(,005L
`The electrolyte amount of 500 µ1 for laminated cells and 750 µ1 for
`I4$ $&$,#.!&3#$ (5!0"# !1 QVV q& 1!. &(5’"(#$7 ,$&&% ("7 XQV q& 1!.
`partially laminated/non-laminated cells is used within an argon filled
`;(.#’(&&3 &(5’"(#$7_"!"D&(5’"(#$7 ,$&&% ’% 0%$7 :’#4’" (" (.<!" N&&$7
`glovebox (M1120, H2O and 0 2 content < 0.1 ppm, MBraun, Germany)
`<&!)$*!B [=9SV@ ESK ("7 KS ,!"#$"# r VLR ;;5@ GO%24!@ g$.5("3\
`and sealed under vacuum. The cells were kept at room temperature
`("7 %$(&$7 0"7$. )(,005L I4$ ,$&&% :$.$ ?$;# (# .!!5 #$5;$.(#0.$
`over night before starting the electrochemical characterization. To
`!)$. "’<4# *$1!.$ %#(.#’"< #4$ $&$,#.!,4$5’,(& ,4(.(,#$.’F(#’!"L I!
`study the effect of additional cell compression, gravimetric force was
`%#073 #4$ $M$,# !1 (77’#’!"(& ,$&& ,!5;.$%%’!"@ <.()’5$#.’, 1!.,$ :(%
`applied to the cells by compressing each pouch cell stack with a weight
`(;;&’$7 #! #4$ ,$&&% *3 ,!5;.$%%’"< $(,4 ;!0,4 ,$&& %#(,? :’#4 ( :$’<4#
`of —2.5 kg on top, while placing a polystyrol plate between the cell and
`!1 lSLQ ?< !" #!;@ :4’&$ ;&(,’"< ( ;!&3%#3.!& ;&(#$ *$#:$$" #4$ ,$&& ("7
`applied weight for homogeneous force distribution along the active
`(;;&’$7 :$’<4# 1!. 4!5!<$"$!0% 1!.,$ 7’%#.’*0#’!" (&!"< #4$ (,#’)$
`single cell area.
`%’"<&$ ,$&& (.$(L
`For half-cell measurements, the electrodes were punched into cir-
`>!. 4(&1D,$&& 5$(%0.$5$"#%@ #4$ $&$,#.!7$% :$.$ ;0",4$7 ’"#! ,’.D
`cular disks of 10 mm diameter and dried at 110 'V under vacuum for
`,0&(. 7’%?% !1 RV 55 7’(5$#$. ("7 7.’$7 (# RRV k 0"7$. )(,005 1!.
`12 h. Half-cell measurements were carried out in three electrode geo-
`RS 4L E(&1D,$&& 5$(%0.$5$"#% :$.$ ,(..’$7 !0# ’" #4.$$ $&$,#.!7$ <$!D
`metry using a Swagelok type T-cell setup, assembled in an Argon filled
`5$#.3 0%’"< ( +:(<$&!? #3;$ ID,$&& %$#0;@ (%%$5*&$7 ’" (" A.<!" N&&$7
`glovebox. Lithium metal was used as reference and counter electrode.
`<&!)$*!BL 6’#4’05 5$#(& :(% 0%$7 (% .$1$.$",$ ("7 ,!0"#$. $&$,#.!7$L
`LP57 was used as electrolyte for NMC half-cell measurements. A mix-
`6GQX :(% 0%$7 (% $&$,#.!&3#$ 1!. J= 4(&1D,$&& 5$(%0.$5$"#%L A 5’BD
`ture of LP57 (98 wt%) and vinylene carbonate (2 wt%) was used as
`#0.$ !1 6GQX [W] :#P\ ("7 )’"3&$"$ ,(.*!"(#$ [S :#P\ :(% 0%$7 (%
`electrolyte for graphite half-cell measurements and for all full cell
`$&$,#.!&3#$ 1!. <.(;4’#$ 4(&1D,$&& 5$(%0.$5$"#% ("7 1!. (&& 10&& ,$&&
`measurements. Half-cells were kept at mom temperature over night
`5$(%0.$5$"#%L E(&1D,$&&% :$.$ ?$;# (# .!!5 #$5;$.(#0.$ !)$. "’<4#
`before starting the electrochemical characterization.
`*$1!.$ %#(.#’"< #4$ $&$,#.!,4$5’,(& ,4(.(,#$.’F(#’!"L
`
`2.2. Electrode/separator preparation
`MNMN 9-$0’%).$X&$,2%2’)% ,%$,2%2’")!
`
`The cathode was prepared by mixing NMC (93 wt%), PVDF (3 wt
`I4$ ,(#4!7$ :(% ;.$;(.$7 *3 5’B’"< J= [WO :#P\@ Gi-> [O :#
`%), Super C65 carbon (3 wt%) and KS6L graphite (1 wt%) with NMP
`P\@ +0;$. TQ ,(.*!" [O :#P\ ("7 C+T6 <.(;4’#$ [R :#P\ :’#4 J=G
`solvent to have a final solid content of 60 wt%. The anode was prepared
`%!&)$"# #! 4()$ ( N"(& %!&’7 ,!"#$"# !1 TV :#PL I4$ ("!7$ :(% ;.$;(.$7
`
`Electrochemical characterization was done with a battery tester
`2&$,#.!,4$5’,(& ,4(.(,#$.’F(#’!" :(% 7!"$ :’#4 ( *(##$.3 #$%#$.
`(CTS-LAB, BaSyTec, Germany), using galvanostatic
`(CC) and
`[ I+D6A9@ O2/(6$0@ g$.5("3\@ 0%’"<
`<(&)("!%#(#’,
`[ \
`("7
`
`2.4. Cell characteritation
`MN>N 8$-- 032%20’$%"Z2’")!
`
`)-*
`152
`
`JLab/Cambridge, Exh. 1030, p. 2
`
`

`

`M. Franlcenberger, et al.
`GN P%2!W$![$%7$%5 $’ 2-N
`
`Journal of Electroanalytical Chemistry 837 (2019) 151-158
`/9=:806"93".621<:90806><5106"-4275;<:>"+(*"#’%&,$"&)&?&)+
`
`potentiostatic (CV) modes for charging step and CC-mode for discharge
`;!#$"#’!%#(#’, [ i\ 5!7$% 1!. ,4(.<’"< %#$; ("7 D5!7$ 1!. 7’%,4(.<$
`step. For full cell measurements, the voltage ranges were adjusted to
`%#$;L >!. 10&& ,$&& 5$(%0.$5$"#%@ #4$ )!&#(<$ .("<$% :$.$ (7c0%#$7 #!
`3.0 V-4.2 V, for NMC half-cell measurements the voltage ranges were
`OLV i^ULS i@ 1!. J= 4(&1D,$&& 5$(%0.$5$"#% #4$ )!&#(<$ .("<$% :$.$
`adjusted to 3.0 V-4.3 V, for graphite half-cell measurements the voltage
`(7c0%#$7 #! OLV i^ULO i@ 1!. <.(;4’#$ 4(&1D,$&& 5$(%0.$5$"#% #4$ )!&#(<$
`ranges were adjusted to 0.02 V-1.5 V. CV charging steps were con-
`.("<$% :$.$ (7c0%#$7 #! VLVS i^RLQ iL i ,4(.<’"< %#$;% :$.$ ,!"D
`tinued until the charging current dropped below 0.05C rate. For the full
`#’"0$7 0"#’& #4$ ,4(.<’"< ,0..$"# 7.!;;$7 *$&!: VLVQ .(#$L >!. #4$ 10&&
`cell experiments, formation was done by applying two cycles at 0.1C,
`,$&& $B;$.’5$"#%@ 1!.5(#’!" :(% 7!"$ *3 (;;&3’"< #:! ,3,&$% (# VLR @
`calculated from the NMC weight and the theoretical NMC capacity of
`,(&,0&(#$7 1.!5 #4$ J= :$’<4# ("7 #4$ #4$!.$#’,(& J= ,(;(,’#3 !1
`168 mAlrg -1. For the further cycling process, C-rates were calculated
`RT] 5A4m<nRL >!. #4$ 10.#4$. ,3,&’"< ;.!,$%%@ D.(#$% :$.$ ,(&,0&(#$7
`according to the measured nominal capacity of each cell, which is the
`(,,!.7’"< #! #4$ 5$(%0.$7 "!5’"(& ,(;(,’#3 !1 $(,4 ,$&&@ :4’,4 ’% #4$
`discharge capacity of the second formation cycle (see supplementary
`7’%,4(.<$ ,(;(,’#3 !1 #4$ %$,!"7 1!.5(#’!" ,3,&$ [%$$ %0;;&$5$"#(.3
`information). For half-cell experiments, the C-rate currents were cal-
`’"1!.5(#’!"\L >!. 4(&1D,$&& $B;$.’5$"#%@ #4$ D.(#$ ,0..$"#% :$.$ ,(&D
`culated to fit to the theoretical capacity of the active material weight
`,0&(#$7 #! N# #! #4$ #4$!.$#’,(& ,(;(,’#3 !1 #4$ (,#’)$ 5(#$.’(& :$’<4#
`:’#4’" #4$ %(5;&$%@ 0%’"< ( #4$!.$#’,(& J= ,(;(,’#3 !1 RT] 5A4m<nR
`within the samples, using a theoretical NMC capacity of 168 mAlrg
`and a theoretical graphite capacity of 372 mAlrg
`("7 ( #4$!.$#’,(& <.(;4’#$ ,(;(,’#3 !1 OXS 5A4m<nRL
`Non-laminated single cell components were prepared for cross-sec-
`J!"D&(5’"(#$7 %’"<&$ ,$&& ,!5;!"$"#% :$.$ ;.$;(.$7 1!. ,.!%%D%$,D
`tion images with a handheld punch (clearance 4 µm, NOGAMI, Japan).
`#’!" ’5(<$% :’#4 ( 4("74$&7 ;0",4 [,&$(.(",$ U q5@ VQA+GD@ /(;("\L
`Argon ion cutting (EM TIC 3X, Leica, Germany) was used for the la-
`A.<!" ’!" ,0##’"< [2= I8 Oj@ 6$’,(@ g$.5("3\ :(% 0%$7 1!. #4$ &(D
`minated electrode-separator stack. A field emission scanning electron
`5’"(#$7 $&$,#.!7$D%$;(.(#!. %#(,?L A N$&7 $5’%%’!" %,(""’"< $&$,#.!"
`microscope (FE-SEM) (Merlin Compact, Zeiss, Germany) with energy
`5’,.!%,!;$ [>2D+2=\ [=$.&’" !5;(,#@ Y$"&&@ g$.5("3\ :’#4 $"$.<3
`dispersive X-ray spectroscopy (EDX) was used to take cross-section
`7’%;$.%’)$ jD.(3 %;$,#.!%,!;3 [2-j\ :(% 0%$7 #! #(?$ ,.!%%D%$,#’!"
`images and EDX element mapping images of a laminated single cell
`’5(<$% ("7 2-j $&$5$"# 5(;;’"< ’5(<$% !1 ( &(5’"(#$7 %’"<&$ ,$&&
`stack.
`%#(,?L
`Porosities of separator and electrode layers were calculated by
`G!.!%’#’$% !1 %$;(.(#!. ("7 $&$,#.!7$ &(3$.% :$.$ ,(&,0&(#$7 *3
`comparing their real volume with the minimal component volume
`,!5;(.’"< #4$’. .$(& )!&05$ :’#4 #4$ 5’"’5(& ,!5;!"$"# )!&05$
`given by the sample weight, using the theoretical densities of the
`<’)$" *3 #4$ %(5;&$ :$’<4#@ 0%’"< #4$ #4$!.$#’,(& 7$"%’#’$% !1 #4$
`components.
`,!5;!"$"#%L
`
`Porosity
`!)+),%-.
`
`pores
`*)+$,
`
`real
`+$"&
`
`real —
`+$"&
`
`components,minimal
`#)’*)($(-, ’%(%’"&
`
`real
`+$"&
`
`(1)
`[R\
`
`For impedance spectroscopy analysis, full cells were charged to
`>!. ’5;$7(",$ %;$,#.!%,!;3 ("(&3%’%@ 10&& ,$&&% :$.$ ,4(.<$7 #!
`3.6 V at 0.1C rate directly after formation. Impedance measurements
`OLT i (# VLR .(#$ 7’.$,#&3 (1#$. 1!.5(#’!"L 85;$7(",$ 5$(%0.$5$"#%
`were carried out in a climate chamber (INCU-Line ® IL 68R, VWR-
`:$.$ ,(..’$7 !0# ’" ( ,&’5(#$ ,4(5*$. [8J hD6’"$" 86 T]H@ U:@H
`avantor, USA) at 25 °C. After connecting
`to the potentiostat
`2#2!’)%@ h+A\ (# SQ k L A1#$.
`,!""$,#’"< #! #4$ ;!#$"#’!%#(#
`(PGSTAT204, Metrohm Autolab, Netherlands), the cells rested for 2 h at
`[Gg+IAISVU@ G$’%)3B +4’)-2[@ J$#4$.&("7%\@ #4$ ,$&&% .$%#$7 1!. S 4 (#
`25 °C prior to the measurement. Impedance analysis was done in po-
`SQ k ;.’!. #! #4$ 5$(%0.$5$"#L 85;$7(",$ ("(&3%’% :(% 7!"$ ’" ;!D
`tentiostatic mode in the frequency range of 50 kHz-10 mHz using an
`#$"#’!%#(#’, 5!7$ ’" #4$ 1.$a0$",3 .("<$ !1 QV ?EF^RV 5EF 0%’"< ("
`amplitude of 10 mV. Data fitting was performed using Z-fit.
`(5;&’#07$ !1 RV 5iL -(#( N##’"< :(% ;$.1!.5$7 0%’"< YDN#L
`
`3. Results and discussion
`5! 6/7(2$7 1#’ ’*7)(77*&#
`
`3.1. Morphological characterization
`KN<N G)%,3)-)7"02- 032%20’$%"Z2’")!
`
`Fig. 2 shows the cross-section SEM images of the non-laminated
`>’<L S %4!:% #4$ ,.!%%D%$,#’!" +2= ’5(<$% !1 #4$ "!"D&(5’"(#$7
`single cell components NMC cathode, self-standing inorganic filled se-
`%’"<&$ ,$&& ,!5;!"$"#% J= ,(#4!7$@ %$&1D%#("7’"< ’"!.<("’, N&&$7 %$D
`parator film and graphite anode.
`;(.(#!. N&5 ("7 <.(;4’#$ ("!7$L
`Cross-section SEM and EDX images of a laminated single cell stack,
` .!%%D%$,#’!" +2= ("7 2-j ’5(<$% !1 ( &(5’"(#$7 %’"<&$ ,$&& %#(,?@
`containing NMC cathode, self-standing inorganic filled (Al2O3) se-
`,!"#(’"’"< J= ,(#4!7$@ %$&1D%#("7’"< ’"!.<("’, N&&$7 [A&SKO\ %$D
`parator film and graphite anode, are shown in Fig. 3.
`;(.(#!. N&5 ("7 <.(;4’#$ ("!7$@ (.$ %4!:" ’" >’<L OL
`The cross-section images of interfacial linking with both electrodes
`I4$ ,.!%%D%$,#’!" ’5(<$% !1 ’"#$.1(,’(& &’"?’"< :’#4 *!#4 $&$,#.!7$%
`clearly show the correspondence with the schematics, as shown in
`,&$(.&3 %4!: #4$ ,!..$%;!"7$",$ :’#4 #4$ %,4$5(#’,%@ (% %4!:" ’"
`Fig. 1. No remaining voids are visible at the interfaces (cathode/se-
`>’<L RL J! .$5(’"’"< )!’7% (.$ )’%’*&$ (# #4$ ’"#$.1(,$% [,(#4!7$_%$D
`parator and anode/separator interfaces) while the separator surface
`;(.(#!. ("7 ("!7$_%$;(.(#!. ’"#$.1(,$%\ :4’&$ #4$ %$;(.(#!. %0.1(,$
`clings to NMC surface particles at the cathode side and to graphite
`,&’"<% #! J= %0.1(,$ ;(.#’,&$% (# #4$ ,(#4!7$ %’7$ ("7 #! <.(;4’#$
`surface particles at the anode side. The high magnification image,
`%0.1(,$ ;(.#’,&$% (# #4$ ("!7$ %’7$L I4$ 4’<4 5(<"’N,(#’!" ’5(<$@
`Fig. 3b and Fig. 3c, show that NMC/graphite particles and separator
`>’<L O* ("7 >’<L O,@ %4!: #4(# J= _<.(;4’#$ ;(.#’,&$% ("7 %$;(.(#!.
`adhere perfectly after lamination. It could be mentioned that no da-
`(74$.$ ;$.1$,#&3 (1#$. &(5’"(#’!"L 8# ,!0&7 *$ 5$"#’!"$7 #4(# "! 7(D
`maging of active materials were found during the lamination process. In
`5(<’"< !1 (,#’)$ 5(#$.’(&% :$.$ 1!0"7 70.’"< #4$ &(5’"(#’!" ;.!,$%%L 8"
`addition, lamination provides stabilized interfaces which minimize the
`(77’#’!"@ &(5’"(#’!" ;.!)’7$% %#(*’&’F$7 ’"#$.1(,$% :4’,4 5’"’5’F$ #4$
`interfacial resistances and reduce the capacity fading upon increasing
`’"#$.1(,’(& .$%’%#(",$% ("7 .$70,$ #4$ ,(;(,’#3 1(7’"< 0;!" ’",.$(%’"<
`the C-rates. The EDX image proves that the electrode and separator
`#4$ D.(#$%L I4$ 2-j ’5(<$ ;.!)$% #4(# #4$ $&$,#.!7$ ("7 %$;(.(#!.
`interface is well contacted. The EDX mapping shows the homogeneous
`’"#$.1(,$ ’% :$&& ,!"#(,#$7L I4$ 2-j 5(;;’"< %4!:% #4$ 4!5!<$"$!0%
`distribution of alumina in the separator (Fig. 3d).
`7’%#.’*0#’!" !1 (&05’"( ’" #4$ %$;(.(#!. [>’<L O7\L
`The overall pore volume within the active area of anode layer, se-
`I4$ !)$.(&& ;!.$ )!&05$ :’#4’" #4$ (,#’)$ (.$( !1 ("!7$ &(3$.@ %$D
`parator and cathode layer in the single cell stack is reduced by -66%
`;(.(#!. ("7 ,(#4!7$ &(3$. ’" #4$ %’"<&$ ,$&& %#(,? ’% .$70,$7 *3 lTTP
`upon lamination. Therefore, the overall porosity of the cathode-
`0;!" &(5’"(#’!"L I4$.$1!.$@
`#4$ !)$.(&& ;!.!%’#3 !1
`#4$ ,(#4!7$D
`
`separator-anode stack decreases from -54% down to -30%. The S