NOVI OBETI NA PODROČJU AKUMULATORJEV ZA e-vozila. doc. dr. Robert Dominko Odsek za kemijo materialov Kemijski inštitut, Ljubljana
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1 NOVI OBETI NA PODROČJU AKUMULATORJEV ZA e-vozila doc. dr. Robert Dominko Odsek za kemijo materialov Kemijski inštitut, Ljubljana Torek, 9. maj 2016
2 Zgodovina baterij BAGDADSKA BATERIJA Okoli leta 1930 so v okolici Bagdada našli lončene posode, ki spominjajo na baterije: domnevajo da so stare več kot 2000 let. Rekonstrukcija je pokazala, da je napetost baterije približno 2V, če se uporabi grozdni sok kot elektrolit. Nikomur ni znano zakaj so jh uporabljali...
3 Zgodovina baterij LUIGI GALVANI Leta 1780 je Luigi Galvani (Bologna, Italy) je pri eksperimentiranju z žabjimi kraki opazil: - krčenje krakov kot posledica udara strele in povzročeno z napravami, ki so proizvajale elektriko; - krčenje krakov, ko jih je priključil na različne kovine brez dodatnega izvora elektrike to je poimenoval elektrika živalskega izvora.
4 Zgodovina baterij ALESSANDRO VOLTA Alessandro Volta (Pavia, Italy) je sklepal, da so vzrok za elektriko telesne tekočine žabe (elektrolit) in različne kovine, in ne žabji kraki -Okoli leta 1800 je naredil prvo baterijo iz izmenjajočih kovinskih diskov, ki jih je ločil z vlažno porozno tkanino namočeno v raztopino soli; -Baterija je omogočala generirati strele podobne tistim, ki so jih dobili s pomočjo naprav, ki so proizvajale elektriko.
5 Zn kisla primarna baterija Leclanche tip baterije E o 1.5V E real 1.0V ANODA Zn(s) Zn e - plinska kletka bitumen separator katodni kompozit (MnO 2, ZnCl 2, NH 4 Cl, in ogljik) grafitna palica cikova pločevina ohišje izolator KATODA NH MnO 2 (s) + 2e - Mn 2 O 3 (s) + H 2 O(l) + 2 NH 3 (aq)
6 Gaston Planté (1859) Pb akumulator PbSO 4 (s) + 2 e Pb(s) + SO 2 4 E o = V PbO 2 (s) + 4 H e Pb H 2 O E o =+1.460
7 Električni avtomobili smo poznali konec 18. stoletja Električen avto ZNAN KONCEPT IZ 18. STOLETJA (April 1899): Prvi avto, ki je bil hitrejši od 100 km/h, je bil ELEKTRIČEN AVTO La Jamais Contente, 1899 USA, leta 1900: 40 % vozil na parni pogon 38 % električnih vozil 22 % motor z notranjim izgorevanjem
8 25 let Li ionskega akumulatorja In 1991 Sony was the first in the world to commercialize a lithium-ion rechargeable battery, forever changing the history of mobile devices.
9 Spremembe v navadah in načinu življenja
10 Princip delovanja litijev ionski akumulator Elektrodni materiali so samo gostitelj litija
11 Separator Al tokovni nosilec Cu tokovni nosilec Komercialni Li-ionski akumulatorji Energija je produkt napetosti in kapacitete e - med polnjenjem Polnjenje e - med praznjenjem Li + Pozitivna elektroda: približno 150 mah/g pri 3.9 V Negativna elektroda: 300 mah/g za grafit Pozitivna elektroda Li 1-x MO 2 Li + M se reducira oksidira Praznjenje Negativna elektroda Li x C 6
12 Komercialni tipi Li-ionskih akumulatorjev Komercialni sistemi 4 različni katodni materiali, anoda je tipično grafit Različne oblike (prizmatične, cilindrične), različna velikost
13 Uporaba Li-ionskih akumulatorjev Vsaka aplikacija ima različne prioritete pri delovanju, čeprav vse aplikacije temeljijo na podobnem principu delovanja Energijska gostota Nizko samopraznjenje Varnost Življenska doba Moč/energija Temperaturno območje delovanja Moč/energija Življenska doba Razmerje življenska doba - cena
14 Zakaj potrebujemo boljše akumulatorje E = f (prostor, čas, vremenske razmere,...)
15 Naše navade Vir: Fraunhofer Vir: Driving_and_parking_patterns_of_European_car_drivers-a_mobility_survey.pdf
16 Potreba po superbateriji 1/ARPA-E-and-the-Quest-for-the-Holy-Grail-of-Batteries.aspx
17 Potreba po superbateriji Električno letalo za 100 potnikov in doseg 3000 km potrebuje baterijo z eenrgijo 1000 Wh/kg 4 krat več kot je imamo danes na voljo
18 Kako povečamo energijsko gostoto Uporaba kovinskega litija kot anode 5V sistemi Katode z visoko kapaciteto (izkoriščanje > 1 elektron, kisik)
19 Akumulatorske tehnologije Potreba po ekonomsko in okoljsko vzdržnih baterijskih sistemih z višjo energijsko gostoto
20 Energijska gostota (LIB) Energy Density / Wh L LIB (v uporabi) baterija Sistem Specific Energy / Wh kg -1
21 Energijska gostota (LIB) Energy Density / Wh L LIB (v uporabi) baterija Baterija * Sistem LIB (optimizacija) Sistem *predpostavimo: kovinski Li Specific Energy / Wh kg -1
22 Kaj se dogaja med polnjenjem? Ko elektronegativnost prehodne kovine narašča => Kisik se vključi v redoks reakcijo E Voltage Li 2s LiMO 2 M - d O 2p DOS DOS
23 Litijirani oksidi prehodnih kovin Ni kapaciteta 100 mah/g zaradi spremembe oksidacijskega stanja na niklju. Li[Li 0.16 Ni 0.12 Mn 0.65 ]O 2 Celokupna reverezibilna kapaciteta 200 mah/g (vključuje kisik) Degradacija: Padec kapacitete in sprememba napetosti. Nastanek kisikovih radikalov, ki reagirajo z elektrolitom.
24 Solid state sinteza Li2IrO3 Sinteza (900oC, 15 h) Peletke Li2Ir1-xSnxO3 x = 0.0 Intensity Mix IrO2, SnO2, in Li2CO3 Visoko energijsko mletje > 40 minut RP = 10.2 % x = 0.25 RP = 7.5 % x = 0.5 RP = 11.2 % Scattering Angle (deg.)
25 Vizualizacija O-O dimerov z TEM O-O razalje: TEM: Struktura na osnovi 1.56 neutronske Å in 1.83 difrakcije Å Neutron: 1.42 Rdeči Å in kisiki 1.86v Å oksidiranem stanju DFT: 1.51 Črni Å kisiki in 1.88 v začetnem Å stanju Modro: iridium Li 2 IrO 3 : stabilna struktura in koordinacija Ir atomov onemogoča nastanek kationskega nereda elektrokemijska krivulja ne spremeni oblike Li 2 Sn x Ir 1-x O 3 : Sn v strukturi omogoča lokalen nered in s tem spremembo oblike elektrokemijske krivulje
26 Povzetek Nastanek kisikovih dimerov je potreben pri napetostih pod 4.3V vs. Li 5 M - kovina: Voltage (V) Li 4 FeSbO 6 Li 4 Fe 0.56 TeO 6 Li 2 Ru 0.75 Sn 0.25 O 3 Li 2 Ir 0.75 Sn 0.25 O 3 Li2 IrO x Li content (% of pristine) Ru Ru, Sn Ru, Mn Ir Ir,Sn Ni,Mn,Co Fe, Sb Ni, Te Ni, Sb Mn Fe, Te Nice Mix Bad Močna kovalentna vez M-O
27 Energijska gostota (LIB vs. PLIB) Energy Density / Wh L PLIB: Post-Lithium-Ion-Batteries Baterija LIB (optimizacija) * LIB (v uporabi) Li/S 600 Baterija baterija Sistem 400 Sistem 200 Sistem *predpostavimo: kovinski Li Specific Energy / Wh kg -1
28 Litij žveplov akumulator Shematična predstavitev Li-S akumulatorja: I II III Področje I: S 8 S x 2 ; x ~ 6 8 Področje II: S x 2 S y 2 ; y ~ 3 4 Področje III: precipitacija Li 2 S R. Dominko, M. U.M. Patel, V. Lapornik, A. Vizintin, M. Koželj, N. N. Tušar, I. Arčon, L. Stievano, G. Aquilanti, J. Phsy. Chem. C, 2015, 119,
29 Litij žveplov akumulator Slabosti Prevodnost žvepla Volumske spremembe Samo praznjenje polisulfidi Možne rešitve Nanostrukturirani materiali separator Zaščita litija 29
30 Sinteza GO in rgo
31 Vizualicacija GO plasti
32 Fluoriran rgo
33 Priprava rgo sloja na separatorju Top-down view Cross section Površino separatorja smo prekrili z rgo-x Konfiguracija baterije
34 Elektrokemija Hidrofoben efekt ustavi difuzijo polisulfidov skozi separator
35 Delovanje Li-S akumulatorja Specific capacity / mah.g Delovanje Li-S akumulatorja v laboratoriju Charge Discharge 1,010 1,005 1,000 0,995 Coulombic efficiency U/ V vs. Li/Li + 3,0 2,5 2,0 0 0,990 1, Cycle Number Capacity / mahg -1 Delovanje prototipne celice po protokolu Dynamic Stress Test simulacija vožnje
36 Energijska gostota (LIB vs. PLIB) Energy Density / Wh L LIB (v uporabi) baterija PLIB: Post-Lithium-Ion-Batteries Baterija Sistem Sistem Sistem LIB (optimizacija) * Sistem Li/S Baterija *predpostavimo: kovinski Li Specific Energy / Wh kg -1 Mg Wh/L = Wh/kg Baterija Li/O 2
37 Mg akumulatorji Največja nahajališča litija so v Južni Ameriki Neenakomerna porazdelitev litija za komercialno pridobivanje GEOPOLITIČNO NERAVNOTEŽJE
38 Lastnosti magnezija Mogoče uporabiti kovinski Mg Magnezij je zelo razširjen in približno 20 krat cenejši Visok redoks potencial V in dva elektrona v reakciji kar zagotavlja visoko energijo H. D. Yoo, et al, Energy Environ.Sci., 2013, 6,
39 Organski Mg akumulatorji Akumulatorji z napetostjo V na celico
40 Vgradnja magnezija v spinel U / V vs Mg/Mg M Mg(NO 3 ) 2 water solution 4,0 3,5 Mg insertion into Li x Mn 2 O 4 Voltage range between 3.5V and 1V I / ma first cycle higher cycles Voltage vs. Mg/Mg 2+ 3,0 2,5 2,0 1,5 Mg insertion U / V vs Ag /AgCl EDX Mg STEM-Annular Dark Field Image (ABF) Mn , Time [h] Mg 12 Mg Mn O O 4 8 Mn Mg
41 Magnezij žveplo akumulator Kombinacija Mg in S elementov zagotavlja okoljsko vzdržnost, obenem pa se energijska gostota približuje potrebam za najbolj zahtevne uporabnike. 3,0 2,5 E vs. Mg/Mg 2+ 2,0 1,5 1,0 0,5 0,0 cycle 1 cycle 2 cycle 3 cycle 4 cycle 5 cycle 6 cycle 7 cycle 8 cycle 9 cycle Capacity (mah/g) SUPERBATERIJA prihodnosti???
42 Kje so meje zmogljivosti baterij?»misliš že, da si dosegel meje svojih zmožnosti, in glej, pritečejo nove sile. Prav to je življenje.«franz Kafka nami so nova obzorja, za katerimi se skrivajo novi koncepti, ki bodo nam ali novim generacijam nadomestili fosilna goriva.«
43 Zahvala European Commission under grant agreement No (EUROLIS) European Commission under grant agreement No (HELIS) 4 letni bazični raziskovalni projekt Program, projekt in mladi raziskovalci
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