Supporting Information

Size: px

Start display at page:

Download "Supporting Information"

Betty Nichols
5 years ago
Views:

1 Copyright WILEY-VCH Verlg GmbH & Co. KGA, 99 Weinheim, Germny,. Supporting Informtion for Adv. Mter., DOI:./dm. High Energy nd Power Density Cpcitors from Solution- Processed Ternry Ferroelectric Polymer Nnocomposites Qi Li, Kuo Hn, Mtthew Robert Gdinski, Gungzu Zhng, nd Qing Wng*

2 Supporting Informtion High Energy nd Power Density Cpcitors from Solution-Processed Ternry Ferroelectric Polymer Nnocomposites Qi Li, Kuo Hn, Mtthew R. Gdinski, Gungzu Zhng, nd Qing Wng Deprtment of Mterils Science nd Engineering, The Pennsylvni Stte University University Prk, PA 1, USA Experimentl Section Chemicl exfolition of BNNSs: g h-bn powders (Sigm-Aldrich) were dispersed in 3 ml DMF (Sigm-Aldrich) under vigorous stirring. The mixture ws then subjected to -h tip-type soniction (17 W, W 3%). The resultnt mixture ws first centrifuged t 3, rpm for min, nd the superntnt ws collected. This step purified the mixture from un-exfolited h-bn powders. Then the superntnt ws subjected to -min centrifugtion t, rpm to precipitte BNNSs. After vcuum drying overnight t 7 oc, BNNSs were obtined. Fbriction of /BNNS polymer nnocomposite films: (91/9 mol.%) powders (Solef 31, Solvy) were dissolved in DMF nd stirred overnight to give homogeneous solution t concentrtion of mg ml-1. The BNNS dispersion ws prepred t concentrtion of mg ml-1 in DMF by tip-type soniction (17 W, W 3%) for 1 h, which ws then mixed in the required rtio with solution. After vigorously stirring overnight, the dispersion ws then subjected to 3-min tip-type soniction (17 W, W 3%) before drop csting on glss pltes. The cst films were first dried t oc for h, nd subsequently peeled off the glss pltes for further drying in vcuum t oc 1

3 overnight to remove trce solvent. The typicl thickness of /BNNS nnocomposite films is round µm. Fbriction of /BNNS/BT ternry polymer nnocomposite films: The BNNS dispersion ( mg ml-1) ws first mixed in the required rtio with solution. After stirring vigorously overnight, the BT powders (verge prticle dimeter: nm, dielectric constnt: ~13, US Reserch Nnomterils, Inc.) were dded into the mixture under tip-type soniction t the power of 17 W. The mixture ws further sonicted for nother 3 min. nd then drop cst on glss pltes. The cst films were dried t oc for h, nd subsequently peeled off the glss pltes followed by drying in vcuum t oc overnight. The typicl thickness of /BNNS/BT nnocomposite films is round 1 µm. Chrcteriztion. TEM (Joel JEM-1F) imges were obtined by plcing few drops of the dispersion on lcey crbon covered copper grid, nd evporting them t room temperture prior to observtion. AFM mesurements were performed using DI Nnoscope IV (Veeco, USA) equipped with tpping probe, nd the smples were prepred by dropcsting onto freshly cleved mic surfce nd kept t room temperture overnight to let the solvent evporte. FTIR spectr were obtined in the ttenuted totl reflectnce (ATR) mode using ZnSe crystl s contct to the smples on Vrin Digilb FTS- spectrometer t room temperture. The Rmn spectrum ws recorded with lser confocl Rmn microscope (Renishw System, 3 nm, -3 mw). SEM mesurements were performed with Hitchi S- field emission electron microscope. DSC ws conducted by using TA Instrument Q differentil scnning clorimeter t heting nd cooling rte of oc min-1. X-ry diffrction nlysis ws studied by use of PANlyticl X pert Pro MPD thet-thet diffrctometer. All dt were nlyzed using Jde softwre with Gussin-Lorentz

4 superposition fitting functions. Tensile mechnicl testing ws crried out on n Instron using N lod cell nd n extension rte of mm min-1. Gold electrodes of dimeter of 3 mm nd thickness of nm were sputtered on both sides of the polymer films for the electricl mesurements. Dielectric constnt nd loss were mesured using n Agilent LCR meter (E9A). Dielectric spectr were cquired over brod temperture rnge (- oc) using Hewlett Pckrd A LCR meter in conjunction with Delt Design oven model 3. Resistivity were obtined under n electric field ( MV m-1) provided by Hewlett Pckrd B pa meter/voltge source nd KEPCO BOP M mplifier. Highfield D-E loops were collected using modified Swyer-Tower circuit, where the smples were subjected to tringulr unipolr wve with frequency of Hz. Dielectric brekdown strength mesurements were performed on TREK P1P instrument using the electrosttic pull-down method under DC voltge rmp of V s-1. Two-prmeter Weibull sttistic. Weibull sttistic cn be described s: P(E) = 1 exp(-(e/α)β) where P(E) is the cumultive probbility of electric filure, E is the mesured brekdown field, scle prmeter α is the field strength for which there is 3% probbility for the smple to brekdown (Weibull brekdown strength), nd shpe prmeter β evlutes the sctter of dt nd higher vlue of β represents higher level of dielectric relibility. Fst dischrge experiments. In typicl fst dischrge experiment, the film cpcitor ws chrged to given field nd through high-voltge MOSFET switch (Behlke HTS1). The stored energy ws dischrged to resistor RL in series with the smple. Since the vrious losses in dielectric mteril should lso be treted s n equivlent series resistor (ESR), the energy dischrged to RL (UR) is smller thn the totl stored energy (U) in the smple, s interpreted by the eqution given below: 3

UR = U RL/(RL + ESR) But when the RL is much lrger thn the ESR, the dischrged energy is very close to the stored one. And lso, ESR will depend on the dischrge speed (or RL).

5 UR = U RL/(RL + ESR) But when the RL is much lrger thn the ESR, the dischrged energy is very close to the stored one. And lso, ESR will depend on the dischrge speed (or RL). In the frequency domin nlysis, ESR(ω) = tnδ/(ωc) where tnδ is the dielectric loss, ω is the ngulr frequency, nd C is the cpcitnce. At the initil time of dischrging (high frequencies) to RL in which most of the energy is relesed, ESR effect is smll. At lter stge (longer time nd lower frequencies) of dischrging process, ESR influence increses. In the fst dischrge experiment presented in this study, ll the smples re chrged to n electric field of MV m-1 nd then dischrge to resistor lod RL Electric Displcement D = k t the sme RC time constnt. U = EdD Electric Field E Figure S1. Schemtic D-E loop of dielectric mteril with the stored energy density (U) represented by the shded re.

b Figure S. ) High-resolution TEM imge of BNNS.

b) Simulted imge from inverse FFT of the mrked re in ).

17 nm 1 nm 1 3 Thickness (nm) 7 Figure S3.

showing the sheet thickness. Although monolyer h-bn is ~.

9 nm for sheet-to-substrte re usully ttributed to

6 b Figure S. ) High-resolution TEM imge of BNNS. Inset: Corresponding fst Fourier trnsform (FFT). b) Simulted imge from inverse FFT of the mrked re in ). The results of both the FFT nd inverse FFT confirm hexgonl symmetry of BNNSs. 3 b Totlly 7 nnosheets studied Number.79 nm.17 nm 1 nm 1 3 Thickness (nm) 7 Figure S3. ) AFM imge of BNNSs nd section nlysis long the red line showing the sheet thickness. Although monolyer h-bn is ~.3 nm in thickness, BNNSs with heights rnging from.7-.9 nm for sheet-to-substrte re usully ttributed to single-lyer s result of the trpped solvents.[1] b) Sttisticl nlysis on the thickness of nnosheets bsed on smple set of totlly 7 pieces of BNNSs.

7 Absorbnce (.u.) 13 /BNNS -1 Wvenumber (cm ) Figure S. ATR-FTIR spectr of pristine nd /BNNS. Upon the incorportion of BNNSs, new peks emerge t nd 1,3 cm-1, nd overlp with the chrcteristic peks of, which should be ttributed to the out-of-plne vibrtion nd in-plne ring vibrtion of h-bn, respectively.[] While the bsorption bnds centered round, 13, 7, 79, 97 nd cm -1 corresponding to the α-phse of PVDF[3, ] remin unchnged, suggesting α-phse is still predominnt in P(VDFCTFE)/BNNS. Intensity (.u.) 13 /BNNS Rmn Shift (cm ) 1 Figure S. Rmn spectr of pristine nd /BNNS. The Rmn spectrum of /BNNS presents one dominnt pek t 137. cm-1 which cn be ssigned to the Eg vibrtion mode of h-bn, gin vlidting the presence of BNNS.[]

8 Tble S1. Weibull sttistic prmeters of /BNNS nnocomposites with different contents of BNNSs. wt.% BNNS wt.% BNNS wt.% BNNS 11 wt.% BNNS wt.% BNNS α (MV/m) β (shpe prmeter) wt.% BNNSs Loss (tn ).1 wt.% BNNSs.. wt.% BNNSs wt.% BNNSs 1 wt.% BNNSs. 3 Frequency (Hz) Figure S. Frequency dependence of the dielectric loss of /BNNS nnocomposites with different filler contents. 7

9 Tensile Stress (MP) wt.% BNNSs wt.% BNNSs 7 wt.% BNNSs 1 wt.% BNNSs 1 wt.% BNNSs Young's Modulus (MP) 3 b 3 Tensile Strin (%) BNNS Content (wt.%) c Figure S7. ) Strin-stress curves, b) Young s modulus, nd c) theoreticl dt of brekdown strength clculted bsed on electromechnicl model of /BNNS nnocomposites with different BNNS contents. The ddition of BNNSs gretly promotes the mechnicl properties of the composites s the Young s modulus of /BNNS composites re found to be fr higher thn tht of pristine, demonstrting n efficient lod trnsfer from the polymer mtrix to the BNNSs which cn be ttributed to the fvorble interfcil interction nd uniform filler distribution. The theoreticl Eb is clculted on the bsis of the electromechnicl model with criticl condition described by the eqution in Figure S7c, where Y is the Young s modulus nd εo is the permittivity of free spce. The curve of clculted vlues plotted s function of BNNS content hs the sme trend s the experimentl results nd shows mximum Eb vlue occurring t wt.% loding of BNNSs, indicting tht the mechnicl property of the composites is virtully key fctor determining Eb. Note tht the experimentl dt of Weibull Eb re much lower thn the theoreticlly predicted vlues from the electromechnicl model. This cn be understood from two spects: 1) Model limittion. Mny polymer mterils do not follow the elstic stressstrin reltionship interpreted by the eqution in Figure S7c, nd would experience plstic deformtion nd mechnicl filure t n electric field fr below Eb.[] ) Electricl conduction. Dielectric brekdown of mterils is usully governed by multiple fctors, lthough the electromechnicl effect hs been regrded s the min brekdown mechnism for PVDF bsed ferroelectric polymers.[] Mterils studied by using the electromechnicl model re in principle considered idel insultors with the ssumption of no electricl conduction under the pplied fields. Electricl conduction, however, cnnot be ignored in rel dielectric mteril, especilly t high fields, nd degrdes drmticlly the brekdown strength of mterils. Consequently, much lower Eb is found experimentlly in comprison to the vlue clculted from the theoreticl model.

10 Composites with BNNS content of: wt.% wt.% wt.% wt.% 1 khz Dielectric Constnt Dielectric Constnt BNNS Content (wt.%) 3 Frequency (Hz) Figure S. Frequency dependent dielectric constnt of /BNNS nnocomposites with different filler contents. Inset shows the dielectric constnt of /BNNS composites t 1 khz s function of filler content. 9

11 exotherm 1 wt.% BNNSs wt.% BNNSs Het Flow (.u.) Het Flow (.u.) exotherm wt.% BNNSs wt.% BNNSs 1 b 1 wt.% BNNSs wt.% BNNSs wt.% BNNSs wt.% BNNSs 1 17 Temperture ( C) Temperture ( C) 1 17 Figure S9. DSC curves of nd /BNNS during the first ) heting nd b) cooling cycle with the rmp of C min-1. The DSC profile shows tht the crystlliztion temperture (Tc) grdully increses from 13 C of the pristine copolymer to C of the nnocomposite with wt.% BNNS s the weight frction of BNNSs increses, which implies BNNSs serve s heterogeneous nucleting gents for. It lso gives n increse in crystllinity from.% of unfilled polymer to over % of the composites with high loding rtios, s clculted from the enthlpy of melting in the heting cycle of corresponding mterils (Tble S). Note tht the crystllinity of the vrious smples clculted from DSC results mtches well with tht clculted from XRD results (Tble S). Tble S. Crystlliztion temperture (Tc) nd crystllinity of the polymer mtrix nd the /BNNS nnocomposites clculted from DSC curves. Smple Tc ( C) Crystllinity (%) 13. wt.% BNNSs 1. wt.% BNNSs 3. wt.% BNNSs.3 1 wt.% BNNSs 7.

12 1 1 Intensity (.u.) 1 1 () BN (deg) (1) (1,) (1) () 3 3 () BN () BN (deg) d (1) (1,) Amorphous 3 (1) () Intensity (.u.) () c Amorphous 1 1 (deg) (1) (1,) (deg) (1) 1 (1) (1,) 1 () Amorphous () Intensity (.u.) (1) Amorphous () b () () Intensity (.u.) 3 Figure S. XRD ptterns of ) nd /BNNS nnocomposites with filler concentrtion of b) wt.%, c) wt.% nd d) wt.%. The XRD ptterns exhibit no obvious chnge in crystl phse upon the ddition of BNNSs, while the mjor diffrction peks from crystlline α phse of PVDF become broder s the percentge of BNNSs increses. A clcultion bsed on Scherrer eqution (Tble S3) revels tht the men size of the crystlline domins for (), () nd (1) fces successively decreses with incresing weight frction of BNNSs in the nnocomposites. It is worth pointing out tht decresing in crystl size does not bring in decresed crystllinity becuse of the growth in number of nucletion centers ssocited with the presence of inorgnic fillers. 11

13 Tble S3. Clcultion of men size of the crystlline domins for (), () nd (1) fces of unfilled polymer nd the nnocomposites. The clcultion is bsed on the Scherrer eqution which cn be written s: K cos where τ is the men size of the crystlline domins, K is dimensionless shpe fctor, λ is the X-ry wvelength, β is the line brodening t hlf the mximum intensity (FWHM), nd θ is the Brgg ngle. The clcultion is performed by using Jde softwre with GussinLorentz superposition fitting functions. D () (Å) D () (Å) D (1) (Å) 1 wt.% BNNSs wt.% BNNSs 9 wt.% BNNSs Tble S. α nd β contents, nd crystllinity of nd /BNNS nnocomposites clculted from XRD results by estimtion from the res of relevnt crystlline diffrction peks nd morphous hol of the polymer mtrix. Smple α (%) β (%) Crystllinity (%). 1.. wt.% BNNSs wt.% BNNSs wt.% BNNSs

14 b 3 wt.% BT 1 wt.% BT 1 X wt.% BT X X X wt.% BT X wt.% BNNSs + wt.% BT X wt.% BNNSs + 1 wt.% BT X X wt.% BNNSs + wt.% BT Tensile Stress (MP) Tensile Stress (MP) wt.% BNNSs + wt.% BT 1 X X 3 Tensile Strin (%) 3 Tensile Strin (%) Figure S11. Strin-stress curves of ) /BT nnocomposites with different lodings of BT prticles nd b) /BNNS/BT ternry nnocomposite smples with wt.% BNNSs nd vried concentrtions of BT. With incresing weight frction of BT, the tensile strength of the ternry nnocomposites with wt.% BNNSs increses grdully, indictive of uniform distribution of filler prticles within the nnocomposites. In contrst, the tensile strength of /BT bers decy t BT concentrtions higher thn wt.%, which suggests tht prticle gglomertion occurs t high loding rtios in the bsence of BNNSs. 13

15 1E11 b 1E Composites with filler content of: 1 wt.% BT wt.% BNNSs + 1 wt.% BT wt.% BNNSs + 1 wt.% BT wt.% BNNSs + 1 wt.% BT wt.% BNNSs + 1 wt.% BT 1 wt.% BNNSs + 1 wt.% BT 1E9 1E 1 Time (s) Electricl Resistivity ( m) Electricl Resistivity ( m) 1E9 BNNS Content (WT.%) P(VDF-CT FE) Composites with filler content of: wt.% BNNSs wt.% BNNSs + wt.% BT wt.% BNNSs + wt.% BT wt.% BNNSs + 1 wt.% BT wt.% BNNSs + wt.% BT 1 Time (s) 1 wt.% BNNSs Electricl Resistivity ( m) Electricl Resistivity ( m) d 1E 1E9 1E 3 1 wt.% BT 1E 3 1 BT Content (wt.%) Figure S. Time dependent electricl resistivity nd the vlues recorded t 3 s of, b) /BNNS/BT ternry nnocomposites with 1 wt.% BT nd vried concentrtions of BNNSs nd c, d) /BNNS/BT ternry nnocomposites with wt.% BNNSs nd vried concentrtions of BT. Pnels ) nd b) show cler trend tht s the concentrtion of BNNSs increses, the resistivity of composites increses grdully. Pnels c) nd d) revel tht the ddition of BT nnoprticles degrdes electricl resistivity, but the ternry nnocomposites still possess higher resistivity thn unfilled polymer, pprently due to the presence of BNNSs.

16 @ wt.% BT.1 3 Frequency 1 wt.% BT..1 e 3 Frequency wt.% BNNSs BT Content (wt.%) Frequency (Hz). wt.% BNNSs wt.% BNNSs wt.% BNNSs wt.% BNNSs 1 wt.% BNNSs Frequency 1 wt.% BT BNNS Content (wt.%) 1 Loss (tn ) f Loss (tn ). wt.% BT. Dielectric Constnt... d 1..1 Loss (tn ) wt.% BNNSs wt.% BNNSs wt.% BNNSs wt.% BNNSs 1 wt.% BNNSs Dielectric Constnt...3 wt.% BNNSs wt.% BNNSs wt.% BNNSs wt.% BNNSs 1 wt.% BNNSs Loss (tn ) Dielectric Constnt c Dielectric Constnt wt.% BNNSs wt.% BNNSs wt.% BNNSs wt.% BNNSs 1 wt.% wt.% BT Loss (tn ). Dielectric Constnt. b Loss (tn ) Dielectric Constnt.3. Figure S13. (-d) Frequency dependent dielectric constnt nd loss of P(VDFCTFE)/BNNS/BT ternry nnocomposites with different filler concentrtions. Dielectric constnt nd loss recorded t 1 khz of e) /BNNS/BT ternry nnocomposites with wt.% BNNSs nd vried concentrtions of BT nd f) /BNNS/BT ternry nnocomposites with 1 wt.% BT nd vried concentrtions of BNNSs. As cn be seen, K nd loss increse with the increse of BT content, while BNNSs reduce K nd loss. 1

17 3 Tensile Stress (MP) 1 wt.% BNNSs wt.% BNNSs wt.% BNNSs wt.% BNNSs 1 wt.% BNNSs Young's Modulus (MP) b Tensile Strin (%) BNNS Content (wt.%) 1 Figure S. ) Strin-stress curves nd b) Young s modulus of /BNNS/BT ternry nnocomposite smples with 1 wt.% BT nd vried concentrtions of BNNSs. With incresing weight frction of BNNSs, the Young s modulus of the ternry nnocomposites with fixed concentrtion of BT increses constntly up to wt.% BNNS nd then decrese with further increse of BNNS content, similr trend to tht shown in the P(VDFCTFE)/BNNS binry nnocomposites. 1

18 . wt.% wt.% BT =1 MV/m =13. wt.% BNNSs = MV/m = c. wt.% BNNSs = MV/m =. wt.% BNNSs = MV/m =.3 =79 MV/m =13.9 Electric Field (MV/m) wt.% BNNSs@ 1 wt.% BT = MV/m =.1 wt.% BNNSs = MV/m = wt.% BNNSs = MV/m = wt.% BNNSs 7 =1 MV/m = wt.% BNNSs =3 MV/m =. Electric Field (MV/m) wt.% BNNSs 3 b wt.% wt.% BT =7 MV/m =.17 wt.% BNNSs =39 MV/m =.1.. wt.% BNNSs =7 MV/m = wt.% BNNSs Probbility of Filure (P) Plotted s: Ln(-Ln(1-P)) Probbility of Filure (P) Plotted s: Ln(-Ln(1-P)) 1 BT Content (wt.%) wt.% BNNSs -. Weibull Brekdown Strength (MV/m) Probbility of Filure (P) Plotted s: Ln(-Ln(1-P)) Probbility of Filure (P) Plotted s: Ln(-Ln(1-P)) Weibull Brekdown Strength (MV/m) 1. wt.% BNNSs =9 MV/m =13.17 = MV/m = d Electric Field (MV/m) wt.% BNNSs =3 MV/m =7.. wt.% wt.% BT = MV/m = wt.% BNNSs =17 MV/m = wt.% BNNSs wt.% BNNSs =11 MV/m =.3 =91 MV/m = Electric Field (MV/m) 1 wt.% BT 3 3 BNNS Content (wt.%) 1 Figure S1. (-d) Weibull plots for /BNNS/BT ternry nnocomposites with different filler concentrtions. Weibull brekdown strength of e) /BNNS/BT ternry nnocomposites with wt.% BNNSs nd vried concentrtions of BT nd f) P(VDFCTFE)/BNNS/BT ternry nnocomposites with 1 wt.% BT nd vried concentrtions of BNNSs. In generl, the increse of BT content leds to reduced Eb, wheres the incorportion of BNNSs enhnces Eb. 17

19 exotherm b 1 wt.% BNNSs + 1 wt.% BT wt.% BNNSs + 1 wt.% BT Het Flow (.u.) exotherm Het Flow (.u.) wt.% BNNSs + 1 wt.% BT wt.% BNNSs + 1 wt.% BT wt.% BNNSs + 1 wt.% BT 1 wt.% BNNSs + 1 wt.% BT wt.% BNNSs + 1 wt.% BT wt.% BNNSs + 1 wt.% BT wt.% BNNSs + 1 wt.% BT wt.% BNNSs + 1 wt.% BT 1 wt.% BT 1 wt.% BT Temperture ( C) Temperture ( C) 1 17 Figure S1. DSC curves of /BT nd series of /BNNS/BT ternry nnocomposite smples during the first ) heting nd b) cooling cycle with the rmp of C min-1. The crystlliztion temperture of /BT is higher thn tht of the unfilled copolymer (13 C), which implies BT nnoprticles lso serve s heterogeneous nucleting gents for. The crystllinity increses drmticlly from.% of unfilled polymer to 3.1% of the composites with 1 wt.% of BT nd wt.% of BNNSs, s clculted from the enthlpy of melting in the heting cycle of corresponding mterils (Tble S). This is lso higher thn tht of either the /BNNS with wt.% of BNNSs (i.e.,.3%) or the (PVDF-CTFE)/BT with 1 wt.% of BT (i.e.,.%). Higher crystllinity is expected to contribute to the enhnced D vlue of the /BNNS/BT ternry nnocomposite s compred to the pristine copolymer. Tble S. Crystlliztion temperture (Tc) nd crystllinity of /BT nd P(VDFCTFE)/BNNS/BT ternry nnocomposites. Filler Tc ( C) Crystllinity (%) 1 wt.% BT 1. wt.% BNNSs + 1 wt.% BT 3.3 wt.% BNNSs + 1 wt.% BT 9.7 wt.% BNNSs + 1 wt.% BT 3.1 wt.% BNNSs + 1 wt.% BT wt.% BNNSs + 1 wt.% BT 7.7 1

20 1 1 (deg) () BN (1)() BT (1,) () (1) (deg) d Amorphous (1)() BT (1,) 1 (deg) 3 () BN 1 (1) 3 (1) () () Intensity (.u.) (1) (1)() BT (1,) Amorphous (1) () () Intensity (.u.) c () (deg) Amorphous Intensity (.u.) 1 () BN 1 (1) (1) Amorphous b (1)() BT (1,) (1) () () Intensity (.u.) 3 Figure S17. XRD ptterns of ) /BT with 1 wt.% of BT nd P(VDFCTFE)/BNNS/BT ternry nnocomposite smples with filler concentrtion of b) wt.% BNNSs plus 1 wt.% BT, c) wt.% BNNSs plus 1 wt.% BT nd d) wt.% BNNSs plus 1 wt.% BT. As cn be seen from the XRD ptterns, the polymer mtrix in ll the nnocomposites remins to be predominntly α phse. The decresed polymer crystl size in the ternry nnocomposites reltive to tht in the unfilled mtrix is lso spotted (Tble S). 19

21 Tble S. Men size of the crystlline domins for (), () nd (1) fces of P(VDFCTFE)/BT with 1 wt.% of BT nd the /BNNS/BT ternry nnocomposites. D () (Å) D () (Å) D (1) (Å) 1 1 wt.% BT wt.% BNNSs + 1 wt.% BT 9 19 wt.% BNNSs + 1 wt.% BT 9 13 wt.% BNNSs + 1 wt.% BT 1 11 Tble S7. α nd β contents, crystllinity nd reltive frction of α phse F(α) of P(VDFCTFE)/BT with 1 wt.% of BT nd the /BNNS/BT ternry nnocomposites clculted from the XRD results. The crystllinity clculted from the XRD results is very close to tht from the DSC results (Tble S). Smple α (%) β (%) Crystllinity (%) F(α) (%)) 1 wt.% BT wt.% BNNSs + 1 wt.% BT wt.% BNNSs + 1 wt.% BT wt.% BNNSs + 1 wt.% BT ) The reltive frction of α phse in the crystlline phse of the polymer mtrix is clculted by using the eqution: F(α) = C(α)/(C(α)+C(β)), where C(α) nd C(β) re the contents of α nd β phses, respectively. For exmple, F(α) for the ternry nnocomposite with wt.% BNNSs nd 1 wt.% BT is clculted s: F(α) = 3./(3.+1.) = 9.7.

The totl stored energy density (U) equls Ue plus Ul. BN BN Absorbnce (.u.) /BNNS/BT BT Wvenumber (cm -1) Figure S19. ATR-FTIR spectr of /BNNS/BT ternry nnocomposite with wt.

22 Electric Displcement D Ue Ul U = Ue+Ul Electric Field E Figure S1. Schemtic D-E loop (dshed line) for dielectric mteril with dischrged energy density (Ue) represented by the re colored in pink nd energy loss (Ul) indicted by the re pinted grey. The totl stored energy density (U) equls Ue plus Ul. BN BN Absorbnce (.u.) /BNNS/BT BT Wvenumber (cm -1) Figure S19. ATR-FTIR spectr of /BNNS/BT ternry nnocomposite with wt.% BNNSs nd 1 wt.% BT. The new pek locted t cm-1 cn be ttributed to the stretching vibrtions in the TiO octhedrl of BT.7 The bsorption bnds centered round, 13, 7, 79, 97 nd cm-1 corresponding to the α-phse of PVDF remin unchnged, suggesting α-phse is still predominnt in /BNNS/BT nnocomposites. 1

23 ... b Electric Displcement (C/m ). Electric Displcement (C/m ). 3 Electric Field (MV/m) Electric Field (MV/m) Figure S. D-E loops mesured under unipolr electric fields of Hz for ) nd b) /BNNS/BT ternry nnocomposite with wt.% of BNNSs nd 1 wt.% of BT prticles. The highest electric field pplied for ech mteril is the respective Weibull brekdown field. /BNNS/BT ternry composite with 1 wt.% BNNS nd wt.% BT Electric Displcement (C/m )... Melt-stretched... 3 Electric Field (MV/m) Figure S1. D-E loops mesured under MV m-1 for melt-stretched film nd /BNNS/BT ternry nnocomposite with wt.% BNNSs nd 1 wt.% BT.

24 Supporting Informtion References [S1] Y. Lin, T. W. Willims, J. W. Connell, J. Phys. Chem. Lett. 1, 77-3 (). [S] R. Geick, C. H. Perry, G. Rupprecht, Phys. Rev., 3-7 (19). [S3] S. Rmsundrm, S. Yoon, K. J. Kim, C. Prk, J. Polym. Sci. Prt B: Polym. Phys., (). [S] M. A. Bchmnn, W. L. Gordon, J. L. Koenig, J. B. Lndo, J. Appl. Phys., -1 (1979). [S] Y. M. Shi et l., Nno Lett., (). [S] X. Zhou et l., J. Appl. Phys. 9, 91 (9). [S7] K. S. Mzdiysni, R. T. Dollof, J. S. Smith, J. Am. Cerm. Soc., 3- (199). 3

Supporting Information

Supporting Information Supporting Informtion Ultrfst nd Stble CO Cpture Using Alkli Metl Slt-Promoted MgO-CCO 3 Sorbents Hongjie Cui, Qiming Zhng, Yunwu Hu, Chong Peng, Xingchen Fng, Zhenmin Cheng, Vldimir V. Glvit nd Zhiming