Graphite Intercalation with Large Fluoroanions Dept. of Chemistry and Center for Advanced Materials, Oregon State University Intercalation http://www.cem.msu.edu/~pinnweb/research-na.htm Oregon State University 2 Intercalation Hosts Ion exchange: (fixed charge density) smectite clay Nax+y[Al2-yMgySi4-xAlxO10(OH)2] layered double hydroxide [Mg3Al(OH)8]Cl metal phosphorous sulfide K0.4[Mn0.80.2PS3] Redox reaction: (variable charge density) metal dichalocogenide Lix[MoS2] layered oxides Lix[CoO2], Nax[MoO3] graphite K[C8], [C24]HF2 Oregon State University 3 Energetics For clays – reaction is ion-exchange: Na+ Mont- + N(R)4+ Cl- (aqu) -> N(R)4+ Mont- + NaCl (aqu) For graphite – reaction is redox: Cx + A -> Cx+ A- ΔHrxn = I (Cx) - Ea (A) - ΔHL Oregon State University 4 Graphite structure Graphite is a semi-metal, chemically stable, light, strong A B A C-C in-plane = 1.42 Å Usually (AB)n hexgonal stacking Interlayer distance = 3.354 Å Source: http://www.ccs.uky.edu/~ernst/ Oregon State University 5 Graphite Intercalation oxidant + + + - This is an acceptor-type GIC Donor-type reduces layers and intercalates cations Oregon State University 6 GIC types Reduction M+Cx- Group 1 except Na Oxidation Cx+An- F, Br3-, O (OH) BF4-, P BiF6- , GeF62- to PbF62-, MoF6-, NiF62-, TaF6-, Re PtF6SO4-, NO3-, ClO4-, IO3-, VO43-, CrO42AlCl4-, GaCl4-,FeCl4-, ZrCl6-,TaCl6Oregon State University 7 Staging and dimensions Ic = di + (n - 1) (3.354 Å) For fluoro, oxometallates di ≈ 8 A, for chlorometallates di ≈ 9-10 A Oregon State University 8 Graphite oxidation potentials H2O oxidation potential vs Hammett acidity Colored regions show the electrochemical potential for GIC stages. All GICs are unstable in ambient atmosphere , they oxidize H2O 49% hydrofluoric acid Oregon State University 9 GIC special issues Anions must be oxidatively stable Larger anions could give larger galleries, wider range of chemistry GICs that rapidly decompose in air or aqueous acid are hard to process further Oregon State University 10 CxPFOS - preparation Cx+ K2Mn(IV)F6 + KSO3C8F17 CxSO3C8F17 + K3Mn(III)F6 (CxPFOS) Solvent = aqueous HF 3.35 A Oregon State University 11 CxPFOS intercalate structure Anions selfassemble as bilayers within graphite galleries Oregon State University 12 PFOS twist angle Chain twist defined by FC-CF tortion angle Oregon State University 13 CxPFOS thermal stability CxPFOS 80 1.0 60 0.0 40 -1.0 20 0 0 200 400 100 2.0 -2.0 600 power / mW mass percent 100 14.0 80 11.0 KPFOS 60 8.0 40 5.0 20 2.0 0 -1.0 0 200 400 600 temp / °C temp / °C Oregon State University 14 New syntheses: chemical method Cx + K2MnF6 + LiN(SO2CF3)2 1,2 CxN(SO2CF3)2 + K2LiMnF6 oxidant anion source 1. 48% hydrofluoric acid, ambient conditions 2. hexane, air dry GIC O O CF3 S F3C S N .. O O Oxidant and anion source are separate and changeable. Surprising stability in 50% aqueous acid. CxN(SO2CF3)2 chem prepn 4 wks 120 15 min Inten / arb units 100 12 min 80 x 8 min 60 4 min 2 min 40 1 min 20 0 15 sec 0.1 15 25 35 2 / deg 45 10 100 reaction time graphite 5 1 1000 1000 0 (h) 55 Oregon State University 16 New syntheses: N(SO2CF3)2 orientation F F F F CxN(SO2CF3)2 echem prepn 6.0 charge discharge e 5.0 b c a 32 + V vs Li /Li d dQ/dV 4.0 21 3.0 4.30 4.70 V vs Li+/Li 5.10 2.0 0 100 200 300 400 500 100 600 Capacity (mAh/g) Oregon State University 18 CxN(SO2CF3)2 - echem prepn 6.0 d CxPFOS (b) V vs Li+/Li 5.5 (a) b e d 5.0 b c a 4.5 CxN(SO2CF3)2 4.0 0 100 200 300 400 Charge (mAh/g) Oregon State University 19 CxN(SO2CF3)2 anion orientation Oregon State University 20 CxN(SO2CF3)2 thermal stability 100 Mass loss / pct (b) (a) 80 (c) LiN(SO2CF3)2 (d) 60 (e) 40 20 0 0 200 400 600 800 t / °C Oregon State University 21 Imide (NR2-) intercalates Anion MW di / Å N(SO2CF3)2 280 8.1 N(SO2C2F5)2 380 8.2 N(SO2CF3) (SO2C4F9) 430 8.3 Oregon State University 22 Other intercalated anions Anion MW di / Å C(SO2CF3)3 411 12.3 SO3C8F17 499 29.5 SO3C10F21 599 33.7 SO3C6F10(C2F5) 461 24.4 Oregon State University 23 Borate chelate GIC’s 1.13 CxB(O2C2(CF3)4)2 Stage 1 1.12 0.85 nm CxB(O2C2O(CF3)2)2 Blue: obs Pink: calc Stage 2 0.78 nm T Unexpected anion orientation - long axis to sheets Intercalation rates Intercalate Anion Temp / °C SO3C8F17 N(SO2CF3)2 N(SO2CF3)(SO2C4F9) N(SO2CF2CF3)2 C(SO2CF3)3 SO3C6F5 20 20 70 70 70 20, 70 Reaction half-life / h 10 0.01 100 500 > 1000 no reaction Oregon State University 25 GIC ambient stabilities stage 2 0.5 TFMI 1 / n' 0.4 3 4 5 6 10 0.3 0.2 PFOS PFEI nitrate (HF) 0.1 sulfate (HF) 0.0 0.01 bifluoride 1 100 10000 time / h Oregon State University 26 Application - IRP strategy 1. Intercalation 2. Removal 3. Optional cycle Targets 1. increase internal volume and disorder not surface area 2. low residual content Parameters: intercalate anion, reduction method (thermolysis, hydrolysis, hydrogenation) Oregon State University 27 IRP charge-discharge irrev reversible • GIC is CxPFOS stage 2 • removal is by heating under N2 for 3 h • rate = C / 20 Oregon State University 28 IRP for Li ion battery anodes 600 capacity, mAh/g e- + Cx + Li+ = CxLi rev. after IRP 500 400 NG, rev 300 irrev. after IRP 200 100 NG, irrev 0 0 200 400 600 temp / °C 800 1000 Oregon State University 29