Production and Characterization of Carbon-Free Bi- Functional Cathodes for the use in Lithium-Air Batteries with an Aqueous Alkaline Electrolyte

Transcription

1 Folie 1 Prouction an Characterization o Carbon-Free Bi- Functional Cathoes or the use in Lithium-Air Batteries with an Aqueous Alkaline Electrolyte Norbert Wagner, Dennis Wittmaier, K. Anreas Frierich Institute o Engineering Thermoynamics Electrochemical Energy Technology Paenwalring Stuttgart Germany GDCh - Electrochemistry, , Mainz

2 Folie 2 Outline Preparation methos Characterization methos Carbon-ree electroes Conclusion

3 Folie 3 Activities Battery-Group (DLR) 11 Scientists, 2 Technicians, 6 Stuents Activities: Characterization o state o the art Li - Ion Batteries (in- an ex-situ) Generation 4 batteries: Lithium - Sulur Lithium - Air Preparation an characterization Source: N AT U R E VO L M A R C H

4 Folie 4 Basic Concept Li-Air Battery Anoe: Metallic lithium Cathoe: Porous gas iusion electroe (catalyst(s), biner, substrate an conuctive agent) Battery reaction or aqueous alkaline Li-air battery: 4 Li + O H 2 O 4 LiOH; Re.: G. Girishkumar, B. McCloskey, A. C. Luntz, S. Swanson, W. Wilcke, J. E 0 =3,45V Phys. Chem. Lett. (2010) 1, 2193 Highly porous, 3-imensional biunctional gas iusion electroe (cathoe) Bi-unctional cathoe catalizes battery reactions: ORR = Oxygen reuction reaction ischarging OER = Oxygen evolution reaction - charging Catalyst layer Substrate Sketch o gas iusion electroe

5 Folie 5 Electrolyte Concepts Li-Air Battery 3 Basic electrolyte concepts : Aprotic electrolyte (water ree) Aqueous electrolyte Soli state Mixe aqueous/aprotic hybri DLR Activities: Bi-unctional cathoes Aqueous alkaline electrolyte e.g. LiOH(aq.) Re.: G. Girishkumar, B. McCloskey, A. C. Luntz, S. Swanson, W. Wilcke, J. Phys. Chem. Lett. (2010) 1, 2193

6 Folie 6 Preparation methos Lab-scale Mi-scale Large-scale membrane roller coating nozzle power supporter Colloial Supension Spraying catalyst aitive Nitrogen Dry Power Spraying Atmospheric Plasma Spraying (APS) Hyraulic Pressing Reactive Rolling an Mixing

7 Folie 7 Preparation methos I: Hyraulic pressing Hyraulic Pressing: Simple an ast process Dry process Solvent ree Almost every power processible Any shape o electroe Variable thickness Suitable or carbon-ree electroes

8 Folie 8 Preparation methos II: Dry spraying Dry Spraying: roller Dry process Solvent ree Coate substrates e.g. macroporous Rhoius metal mesh, metal oams Variable thickness membrane coating nozzle Catalyst layer = catalyst+carbon/ graphite+biner power s uppo rter catalyst aitive Nitrog en Various substrate Especially suitable or carbon contenting

9 Folie 9 Preparation methos III: APS Atmosheric Plasma Spraying (APS): Synthesis o catalysts via nitrate solution Oxie catalysts e.g. Co 3, Mn 3, NiO Coate substrates e.g. macroporous Rhoius metal mesh, metal oams Thin catalyst layer possible

10 Folie 10 Characterization methos: In- an Ex-Situ Electrochemical Characterization SEM XRD/XPS Electric Conuctivity Electrolyte CV EIS

11 Folie 11 Carbon-Free Bi-unctional Electroes Carbon is inexpensive, available, non-toxic, catalytic active or ORR an elec. conuctive Most reporte electroes base on carbon material ue to properties! Problem o carbon material! : High carbon corrosion at potentials > 1.35V vs. RHE resulting in structural ecomposition o electroes an ecreasing current ensities ue to the loss o active material! DLR goal: Complete substitution o carbon materials to enhance stability o electroes! Decreasing current ensity

12 Folie 12 Carbon-Free Bi-unctional Electroes IrO 2, Co 3, Mn 3 an La 0.6 Ca 0.4 CoO 3 are most promising bi-unctional catalysts Further investigations: Co 3 most promising oxie catalyst, comparable results to high cost catalyst IrO 2 D. Wittmaier, T. Danner, N. Wagner, K. A. Frierich Screening an urther investigations on promising bi-unctional catalysts or lithium-air batteries with an aqueous alkaline electrolyte, Journal o Applie Electrochemistry (2014) Current ensity / ma cm -1 mg La 0.6 Ca 0.4 CoO 3 La 0.8 Ca 0.2 CoO 3 LaCoO 3 Co 3 Mn 3 25 C 0-2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 Potential vs. RHE / V Substitution o carbon by electrochem. stable, elec. conuctive + catalytic active material to support Co 3 + maintain elec. conuctivity Possible materials ue to alk. electrolyte: Ag an Ni Combinations Ag/Co 3 an Ni/Co 3 Current ensity / ma cm -1 mg La 0.6 Ca 0.4 CoO 3 La 0.8 Ca 0.2 CoO 3 LaCoO 3 Co 3 Mn 3 50 C -6 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 Potential vs. RHE / V

13 Folie 13 Basic concept Li-air battery: Type I (Ag) Combination exhibits high current ensities Variation o Ag/Co 3 ratio to in optimum composition; Biner content 10 wt.-% constant 20 wt.-% Co 3 optimum catalyst content High current ensities + synergetic eect o Ag an Co 3 leas to higher current ensities or ORR + OER compare to pure Ag or Co 3 electroes (not completely unerstoo yet) D. Wittmaier, N. Wagner, K. A. Frierich, H. M. A. Amin, H. Baltruschat Moiie carbon-ree silver electroes or the use as cathoes in lithium-air batteries with an aqueous alkaline electrolyte, Journal o Power Sources (2014) D. Wittmaier, N. Wagner, H. M. A. Amin, H. Baltruschat Biunktioneller Katalysator als Kathoenmaterial ür ie Metall-Lut-Batterie, Patentnummer (2014) Current ensity / ma cm -2 Current ensity / ma cm ORR 119,5 119,5 115,27 48,55 43,9 32,83 120,5 120,15 108, Content Co 3 / Gew.-% OER 51,43 50,03 47, Content Co 3 / Gew.-%

14 Folie 14 Carbon-Free Bi-unctional Electroes: Type I (Ag) Ag Co3O4 Ag Co3O4 FIB-SEM Ag / Co3O4, 20 wt.-% [University o Ulm] SEM Ag / Co3O4, 20 wt.-% [DLR]

15 Folie 15 Carbon-Free Bi-unctional Electroes: Type I (Ag) Comparision o Ag/Co 3 electroes to high cost Ag/ IrO 2 combination (benchmark) 20 wt.-% IrO 2 also highest current ensity High improvement over pure Ag; Ag/Co 3 combination improves ORR activity Comparison shows only slight avantage o Ag/ IrO 2 electroes (in OER) but much higher costs Current ensity / ma cm wt.% Co 3 20 wt.% IrO 2 Pure Ag ORR OER Ag/Co 3 most promising combination or uture investigations Potential vs. RHE / V D. Wittmaier, N. Wagner, K. A. Frierich, H. M. A. Amin, H. Baltruschat Moiie carbon-ree silver electroes or the use as cathoes in lithium-air batteries with an aqueous alkaline electrolyte, Journal o Power Sources (2014)

16 ll bbb eee bbb nnn hhh bbb ll aaaa cccc m mm a jj aa jjj Folie 16 Carbon-Free Bi-unctional Electroes: EIS, Type I (Ag) Recore impeance spectra were moele with equivalent circuit moel R 1 R 2 R 4 L 1 R 5 Dierent moels or ORR an OER CPE 1 R 3 CPE 3 OER moel takes into account growing oxie layer on surace o electroe while electroe operating in OER moe CPE 2 ORR OER Evaluation o important resistances R total or ORR an OER an R 5 (oxie layer) Z / phase / o 135 a a aa a e aa e mmmmm a e mmmm a jc jc j cc je j g j a g gg g c j j gjk a jg kaaa gg jkk j gj ka gg j ma gg jkk aa gg j mmmm a o o j j kk aa g j aa oo e c o c gg j j ka ggj l l j kk aa j l 90 c g j c gg jkk aa gg j l oo j a gg jk a gj ma b i b i i l c i a g jkk aa n i occcc no i le gg j mm aa b l oc aa gg j i i nn oo n i no c i n k i b oo cc b i l o e i l o c g jm a nnnb b bb a c gg kk i b a i c e e a nn oo cc i l gj kk i gj hh kkk kk i h ee i aa no c aa h hh lbb k mmmmm l ee i nn l oo cc i l o cc mm aa gg ee hhh i lo eb jm n bbb eee b c kk hh mmm l e b c hl i nn oo cc i l oo c j i gj k l c a e gg h kk a i cc h l bb i no c i j e h k nb lo c a aaj k h i kk m l n c ee i o cc e i gg j j n kk k a b cc i o g hh kk n l oo c b il c aa e j a kk hh mmm l b ee n gg j b i n k kk kk k kk kk l il oc aa j gg j aa j gj a gg j j gj ggggg a c i nn oo kkk kk j b h l bb gg hk il mmmmmmmmmmmmmmmmmmmmmmmm aa en o a jaa j gg jaa j gj a gg j j b c aa gg jaa j jmmm aaaaa jj jj mm e cc i l eh m hk n b il o c e ab cc no a mmm lb eee hh kk nn il oo bbb cc b eh l no il hk e 45 a b e hh l n n il o c e l bb e hh kk ee nn b cc nn cc il oo aa bb ee hm le il b c hmmm lb nn ee hk n i loo cc e i l ab bb hh lb hk n n i lo c nn i aa bb ee l oo cc i l l bb nn e hh kk nn i l oo cc il h m n il oc b nn aa bb l il oo cc il n il oc e nn il oo cc il b mmmm nn il oo cc lb il n nn cc nn n cc ii nn cc nn ee h il oc k il oo cc il il oo cc il il oc e n il oo cc il il oo cc il bbb ab el hk n hh l hk n aa bb ee l bb ee hh kk nn be hh mm lb aa bb ee e lbb ee hh kk nn hl ab e lbb ee hh kk nn aa ee l hh lbbb eee hhh kkk nnn aa l l ee hh ab el bb ee hh kk nn bb aa ee l e hlbb hh ab l aa lbb hh l mmmmmmmmmmmmmmmmmmmmmmm ee hh kk nn e ee ee hh kk nn ee aa lbb hh kk ee nn hh l e ab lbbb eee hhh kkk nnn hl ee aa ee hh l lbb hh ee kk nn ee aa ee hh l l ee hh kk nn bb e ab ee hh l ee aa l hh kk ee nn bb eh l ee aa bb l hk en b aa aa aa b b bb b bb bb b bb bb b b bb bb b bb bb cc cc cc b e e e ee ee gg gg gg gg h h hh h h hh h h i i k k kk l l k l kk l ll m lll mmmm kk k kk kk k kk l l k l mmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmm kk kk k kk kk mmmmmm l l l l n n nn n nn nn nnnnnn nn n nn nn n nn l kn oo oo ooooo o oo o oo l l l aa bb a aa aa a aa aa a aa a aa aa bbb bb bb bb bbb bb cc c cc cc c cc cc c cc c cc ee eee ee nn ee nn ee eee ee eeee eee ee ee eee g g gg hh hh kk hh kk hh kk hhh g gg gg g gg gg g gg hhghhgg hh gghhh hhh g gghh gghh ghh i i i i i i i i i i i i i i i i i i ii i i i i i i i j j j j j j j j j j j j j j kkk j j kk j jkk j jkk kkk j jkkk j j jkk l l l kk l l l l l l l l nn b b bbb bb bb bb l l nnn bbb nnn l l nn l lnn l lnn l l l l l jl jl kki jl kk ij gg l ij l mmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmm nnn nn nn o o oo o oo oo o oo oo ooo ooo oo o oo oonn o a a aa a aa aa a aa aa a aa bb a bb aa bb aa bbb a aa bb c c cc c cc cc c cc cc cccccc cc e e e e e ee e e e ee ee e ee e ee c e cc ee cc aa ee bbc a e nn bb oo cc aa ee hhh kkk nnn bbb ij oo cc gg laa l ij l l ee hh ij o c b kn gl a e l ee hh kk nn bb ij oo cc bb kk nn gg laa ee eh ij l l ee hh kk nn bb ij o c b kn gl a e ij oo cc gg laa ee hh kk nn bb ij l ij oo cc bbbbb b aa bb ee e gg laa ee hh kk nn bb ij l ijoooooo cccccc k g aaaaaaaa eeeee lll kkk nnn hhhhh ii jj g hh h jj l ak no c l l l kk nn l gg ii ggggg hh ee i ihh i igg h j kk nn ll j kk nn bb jl e joo cc lee kk nn bb jl joo cc aa lee kn e bj i l 0 100m K 3K 10K 100K requency / Hz llll Z' / e e e e e e e e e e b a a b b b a aa aaaaaaa bbbbb a aaaaaaa aaaa nn b bbbb cc c cc ccc eeeee eeeeeeee b hhhhhhhh i igggggggg j j bbbb ggg gg hhhhhh ii iill m iiiiiiii nnnnnn ll jj kk i jj llllllllllll b bb nccccccccccccccccccc lll iiii jjjjjjjj ggg g hhh bbbbbb iiiiii mm nnnnnnnn jjjj kk kk hhhgggg kkkkkkkkk n kkkkkk nn mmmmmmmm nn eeeeee bbbbbb oooooooo eee oooooooo aaaaaaaaa ee e bb o kkk eeeee aa ccc bbb gi i i i g ggg j nnnn j j j j j j gg hhhhhhhhh gg hh hh ii i ii kk i ii j jl l j i l l l l l l l l l l j j j ii j ggg j hh i ii i gg i gg iii j l nn kkkkkkkkkkkkk kkk mm l ll mmmmmmmmmmmmm o a b a aa aa a a a b b c c c c aab c oo b b e cc c e n oo m n l l ll jj m nn j l jjjjjjj l kkk nn o lll nn oo oooooooooo a bb oo oo mmm nn oooo jjj aaaaaa ggggg mmm c c ccc ccccc c eeeee e eeee cc a a a a a Z'' /

17 Folie 17 Carbon-Free Bi-unctional Electroes: EIS, Type I (Ag) Resistances gaine rom simulation o impeance moel: 1000 Co 3 20 wt.% pure Ag IrO 2 20 wt.% Current ensities or ORR only slight ierence, this correspons to values or R total, ORR Current ensities or pure Ag electroes in OER much lower than or also correspons to R total, OER Best combintion or OER exhibits lowest resistance R 5 or oxie layer Ag electroes have highest resistances or OER Resistance total / Resistance total / Co 3 20 wt.% Current ensity / ma cm -2 1 pure Ag IrO 2 20 wt.% R total, OER R total, ORR Current ensity / ma cm -2 Resistance R 5 (Oxie Layer) / D. Wittmaier, N. Wagner, K. A. Frierich, H. M. A. Amin, H. Baltruschat Moiie carbon-ree silver electroes or the use as cathoes in lithium-air batteries with an aqueous alkaline electrolyte, Journal o Power Sources (2014) Co 3 20 wt.% IrO 2 20 wt.% pure Ag Current ensity / ma cm -2 R 5

18 Folie 18 Carbon-Free Bi-unctional Electroes: Type II (Ni) Combination exhibits high current ensities an high stability Variation o Ni/Co 3 ratio to in optimum composition; Biner content 10 wt.-% constant 20 wt.-% Co 3 optimum catalyst content (as or Ag an IrO 2 ) High current ensities + synergetic eect o Ni + Co 3 leas to higher current ensities or ORR + OER compare to pure Ni or Co 3 electroes (not completely unerstoo yet) Higher current ensities or OER than ORR but lower than Ag/Co 3 D. Wittmaier, S. Aisenbrey, N. Wagner, K. A. Frierich Carbon-ree nickel/cobalt-oxie cathoes or lithium-air batteries with an aqueous alkaline electrolyte, Electrochim. Acta (2014), submitte D. Wittmaier, N. Wagner Biunktioneller Katalysator un Leitzusatz als Kathoenmaterial ür ie Metall-Lut-Batterie, Patentnummer (2014) Current ensity / ma cm -2 Current ensity / ma cm ,01 Pure nickel 5 wt.-% Co 3 Pure nickel 5 wt.-% Co 3 16,14 10 wt.-% Co 3 20 wt.-% Co 3 30 wt.-% Co 3 40 wt.-% Co 3 15,17 17,94 10 wt.-% Co 3 20 wt.-% Co 3 30 wt.-% Co 3 40 wt.-% Co 3 25,75 30,58 33,97 44,76 ORR 18,85 20,17 0 % 5 % 10 % 20 % 30 % 40 % Electroe Co 3 content / wt.-% OER 37,69 36,71 0 % 5 % 10 % 20 % 30 % 40 % Electroe Co 3 content / wt. %

19 Folie 19 Publications Peer-reviewe publications: D. Wittmaier, T. Danner, N. Wagner, K. A. Frierich Screening an urther investigations on promising bi-unctional catalysts or lithium-air batteries with an aqueous alkaline electrolyte, Journal o Applie Electrochemistry (2014) D. Wittmaier, N. Wagner, K. A. Frierich, H. M. A. Amin, H. Baltruschat Moiie carbon-ree silver electroes or the use as cathoes in lithium-air batteries with an aqueous alkaline electrolyte, Journal o Power Sources (2014) D. Wittmaier, S. Aisenbrey, N. Wagner, K. A. Frierich Carbon-ree nickel/cobalt-oxie cathoes or lithium-air batteries with an aqueous alkaline electrolyte, Electrochim. Acta (2014), submitte T. Danner, B. Horstmann, D. Wittmaier, N. Wagner, W. G. Bessler Reaction an transport in Ag/Ag2O gas iusion electroes o aqueous Li-O2 batteries; Experiments an moeling, Journal o Power Sources (2014) H. M. A. Amin, H. Baltruschat, D. Wittmaier, K.A. Frierich Highly eicient biunctional catalyst or alkaline oxygen-electroes base on a Ag an spinel Co3O4 hybri: RRDE an online DEMS insights, Angewante Chemie (2014) submitte Patents: D. Wittmaier, N. Wagner, H. M. A. Amin, H. Baltruschat Biunktioneller Katalysator als Kathoenmaterial ür ie Metall-Lut-Batterie, Patentnummer (2014) D. Wittmaier, N. Wagner Biunktioneller Katalysator un Leitzusatz als Kathoenmaterial ür ie Metall-Lut-Batterie, Patentnummer (2014)

20 Folie 20 Conclusion Most promising bi-unctional catalysts Co 3 an IrO 2 Due to carbon corrosion carbon-ree electroes promise higher (longterm) stability Substituion o carbon by Ag an Ni. Electroes prepare with in comparision to IrO 2 low cost Co 3 20 wt.-% Co 3 carbon-ree electroes show highest current ensities Thank you or your attention!

21 Folie 21 Thank you to an our project partners o