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REPORT DOCUMENTATION PAGE nave "ny Bogen Rept Masch 2004 4 Sop 36.2004 Rolacats Tssolymess for Energy Sloss apace SONS No0OL4 04 L909 [ cnawr none ———— [= rca EPEAT wine ——— iin Zhang ean Stale Universi 1a Macrae Revere Labortory unity Pa BA 102 ames Pal Aamo Off of Naat Rass Salton Coute Taner Ont Fe Hern Quincy St Acogto VA TERRORS KERNS —] Apel oc Pubic Release iebuson is United a ks peor, tena State, RS Technolgies, nd DCL working ogter opto etnicy fvetinin co vation oes ‘lac tth euel cea epesyi fo energy tre ngontos, Tata eran ar nyes of MULE TEE CPE) vin fren congctons have hee ates nd smc Ueb tenpelyers boven fate nothin hsm Be eeu energy dest, the AC and DC sro he epyion ee Fore peste a raffle at meovemrt ike beaowm eneagth ad gil ua Ue urpolvve ing mere usa a high tae a is speed iesturge ie hes bon dagaod aod but. Tho sul aerate flowing, vw uw we w (Grane Za Brena Relaxor Terpolymers for Energy Storage Capacitors March 2004 - December 2004 Final Program Report of NUIOLA4-1-0292 Program Manager Dr. Paul Armistead ONK 331 Physical Sciences Polymer Science Programs 800 N. Quiney St Arlington, VA 22247 Submitted by Gi 19 Zhang 187 Matoriats Research Laburatury ‘The Pennsylvania State University University Park, PA 16802 Ph: 814-863-8994 Bax: S1A863-78465 Wesley Hackenberger ‘TRS Technolngles, Inc. 2820 Bast Cullege Avenue State College, PA 16401 Hleetronie Concepts, January, 2005 20050124 069 Summary: | this program, Pena State. TRS Technologies, and CK working together ta perfarm a preliminary investigation on various issues relstad tothe ferrcloetrierelaxortecpalymer for energy slorage capacitors, In chis program, tespolyavers of P(VDE-10KE-CFE) with different compositions heve been synthesized and some of Liew: lerpelymers bave Been, fabricate into thin fms at ECl; che electric energy density, ke AC and DC sesistivities af die terpolymers have boon characterized; and gravefulfsilure and improvement inthe Dreakdowe sirengia and groccful failure of the terpolymer films were investigated; a high voltage and high spend discharge circuit has been dasigned and built, The result are sumutacized io the followin, 1. Terpolymer synthesis and evaluation During this time periad, 5 differen: compositions of P(VDI-TERE-CHE) have been symhosized: T8T.15, 16, 17, 18, and 19, The enmpositians of these weipolymers and bateb size are sunamerizel iy Table 1. or the easy comparison with PCYDIVT#C#) copolymer and ‘radiated copolymer, compositions are alsa weiten in (VDB/TCFECEB in (w/(1-2)9 in the 4 column af the Table} Table 1: Polymer Composition Beh size Composition iu (VDP/TTEVCFE units ISLIS: 65 85 grams GA.SASS/T FSLI6: 61530982 1 ky 6TRBBI TLI7: 64327081 1 ky OROB.L ISLES: 42050868 245 grome 4654/68, TSLI9: 48.1/45.716.2 10D grams SL348.716.2 ‘The dielectric properties ofthese camipositions have hoen characterized. The overalt LGlva que'ity was also cvaluated and it was found that the resin repreduciitity is still an issue and resin quality fs very sensitive in the synchesis parameters which are noc welt understood au his scage, especially for terpolymers at composition of VDIF/TrHE: ratio near or helosy ‘S(VS0mol, Purthermere, the synthesis pararaeters for the terpolymer with lower VDBTWEE ‘ato are very different from those with higher VDE/TEPE eatin (for examplo, when using the synthesis parmeters of IST.I7 10 syathesize ISL18, both ute resin quality and composition ‘uniformity are nol high). We intend to do x synthesis scudy in the fucue to understand how the synthouis parametees change with the composicon and influence the rexin quality "The purpose af synthesis crpolyroers with VOE/LEE ratio at or below 30/50 mot is to lower the weak field dislcctic eunstunt so that the encrgy density at high field cau surpsst those with VDEPIcHE mute reco higher than thal. Tn deeded, the wesk fic dielectric onstant of ISL1B und TST.19 is Towered (es shows in igure 1 which is a compurisan of the Figure L, Dictate auntaat af a function of tenperaare for ISE.18 (46/54/53 mol) aad the Cexpalyning of A3317.5 mol, Hy lowering the WDE/TPFE mol cto t0 neat or bein 50450 %, the weak Geld Cieleee cormtnt fs lowered along withthe lose. dielectric oonstent between ISL18 and ISL14), Because of poor resin quality, the breskdowr. field for TSEI8 and ISL19 is below 200 MVén (compared with the otter compositions (SDEALET mole rate higher han 83°97) for which -he resin qualily is mach boter and the breakdoven field ean reach above 400 MVim). Howver. itis noted that the energy density at lower ficld for ISL18 and 181.19 is reduced compared with othor terpolymer compositions ‘which indicstes a reduced polarization saturation effect as intended, Further improvement in the synthesis conditions for the terpotyraers in the lower VDEITEFE mot% will be made in the Tatore 50 that high ditectric strangdh can be achieved. (SLIB also shows a high AC conduction as indicated by the inceeased {ow frequency (10D Hz) dielectric constant aid last at temperatuces above 7U°C). 2, ‘Terpolyiner film fabrication at ECI Comeally, there are 3 batches of ter compositions which have enough ei rami) to predace films at ECT using their dram cast machine, In the mile of August, 04, BCT hss produeed {lms of 15 yun thick of ISLE (G33777.5 men) using their drum east set-up. ‘The fms reveived are shown in figuee 2. ‘The fotal length of the films is 280 feet with the initial 50 feet not usable (for adjusting the. cast parameters). A 250hwatt IR light 6-8" from the film surface maving at $ feet per mumute helped to dry the flm a litle, ‘Tho width of the fm is 5° and dhe center 3.4" of fl width has good quality dronghoot (when inspected using ‘optic method). The vesia quality of ISL17 Figwe 2 the shin fas (28D fect ons! of doce now atlow foe high quality fli to be ‘polymer 48.5 mol lubricated at OC ‘produced using the drum cast mctliod at BCE ‘Currently, we are evaluating ISL16 to determine wheter i is silable for drum cost at BC 3. Energy density, DC and AC eontluctivity, and uther related properties (31) Boergy density messured from the polarization loop at 10 Hz and AC:aad DC coruducivily ‘As a non-linear dielectric polymer, the stored and =) electric energy “densiry showld be lealated from Use [EAD , where in the nrfuce charge density (elect displacement which i ig the same as the polarization for the: polymers dtisipted jnvestigated arc). Using the polarization Inysteresis Loop measored wader unipolar condition, the stored and discharged energy density can be ° WE ahtained as schematically shovee in figure 3. Figure Penn 3 is for the tempolymer (VDE-ATEE-CFE) pi 9, Detonation ofthe deca! dash ols ected 10 Hz and te snes SEENS, Osten of eae Strats ths didungedcncay deity Tre eaclsed Geazt) aes ey Glo a anil washed sre represents the energy divsiutel, The lola stored energy density is the swramation of the discharged energy density plus the dissipated energy deusity, from which the effcioncy of the dislectic film (or a capacitor) can be dezerincd, In this expetiment, ‘he applic field B increases from 2era toa saaximum value (charging the capacitor) and then. is reducod to zoo (the capacicor discharge. If chere fs no conduction loss. the chatge density at BaD at the ond of discharging cycle stouid be the samo as that at the boginning of che charging cycle, Due to AC conduction Toss, the polarization at FeO aller tho hirgingllischarging eyele does nol eetuin to Une initial value, Therefore, his aliTenenee in the polarization (or charge density) at f=frhetwveen the heginaing and ending ofthe cycle isa magcre of AC conductivity in dhe film (or capacitor). The experimental data show that chis AC conductivity is sensitive ca the film processing condition (such as the salvent used and ‘anacaling condition) and also Uw sess: applied during, the measurement in attion to th vesin quality. More importantly, the moisture ubsotbed gun greatly increase this AC lO ‘- il ie ‘Figure 4. @ Figure 4. (b} onduetion loss. Figure 4 ilustates how chis AC conduction loss depends on the procesying ‘ution for P(VDP-TeFE-CHE) 70/30/8.1 mol (differcot solvents, annealing conditions, ft applied Jaca! sttess daring the mcasurement). The data slso indicate dat in these lerpalyimers, in addition to the AC conduotion, there is also intrinsic dielectric loxs owing to the ferroelectric nature of the polymer. We are in the process to () evaluate Low the AC ‘conductivity af the terpolymer depends on the film processing nal measurement coadidons and (il) compare the AC conductivity ofthe lerpalymers with other polymers, aspectally the commercial P(VDP-TEFE) vopolymers, It was found that moisoore absorbed by te tespolyrmer can caise both the AC and DC conductivity quite markedly. It was also found that in same well proparcd trpulymer [las the AC conduction can reach the levet of the commercial copolymer. How tp reduce the inttinsic AC conduction Joss und ferroelectric Anysterosis loss ssn ares te investigaoed ithe future DC vorductviry was also evataated for soveral polymers {all hewsured under 100 ‘V) and iv su:nmatized in Table 2. As the twference, the DC conductivity of the comuarcial PYDE copolymers is also incfoded. The eonunersial PVDF cupulyierfitms wese fabricated foam the resins obtained using the same solution cast mothod as that to fabricale the teepotycaar fits. It seems the DC conductivity of the cerpolymers is nesrly the same as that of the commsreiat PVDF vopalyiness processed under the same exmditions. Tu the future. che ccomeaereil capolymer films will be acquired and used forthe: comparison ‘Table2_ DC rcsitvity of erpelyeners as well as compiz with the Mercia oapalymers 7 Polpraers De Resistivity (asm) ‘Coaamerial copalymers Onn PLVDE-TFB) 65/35 solotioa ast (DMF) Txio* Fixe (ODF FR SO/T solution wed (PMP) EFS wee yok: presed fms [xt ‘fapoiyaes i TEL 14: P{V DE FE CH) COT. colton cast DMP| ‘Solutian case MEK| Meli-pressed fils | ISLI7 RVDE-TaFE- CFT) 700/81 solution cast DME ‘fable 3, “ho discharged energy density and efficiency from the mnipelar poterization loop mcasurement for the to corpolymers charzcteriz (eormsesion | Eleerie | Releised | Contoncd Teo i Field Brgy | Trespy | Eificieney TENE avin) | dten grew) to 15-5, gala 30 167 O78 siete 327 a eases 7s 1 06 ' en [oe H a clecsnale 377 ' 3a essns [38 sez Fe enins F 2 mo} 0 Figure 5 presents the charging and discharging curves of the _tespolymer 63/7773 mol measured at 10 Hz under different applied fietd level (400 MV/an is the highest ficld measured). From the data, the discharged energy density und efficieney are detorainod. For This iim, Ghe electric energy density is 8.9 Tey? under 400 RtVien with an. cfficiency of 7196. The data are summarized in Table 3, In the lable, the measured results Irgcn ISLS (6525/8.5 mol) are also includ. Ie noted that che electrades use alr affect the efficiency (mainly through the charge Injevtior ofthe inerlice und heawe AC eunduction less) Figure 6 presencs the discharged energy deesity for 63/37/7.5 nol messurce on to samples (erasses fxd agen citles) and for 6852.9 mol which can reach 10 Yon" under } i Figure 6. (a) Figure 6,"@) 350 Mien, These results along th the dua in Tulle 2 indicate chat both VDEVTIFE ratio 2s well a CFE mol% will affect the discharge energy density. More eliaracterizaion over broad composition range and processing conditions will be necded to establish general guidance on ‘he energy density and efffciency inthis class of polymers, Pulse dischatge meaturement ofthe discharged energy density from the eepolyners . ‘As a fitst step to measure the ky high voltage high apecd discharge characteristics of these terpolymers, w high speed high voltwge amplifier eirauit wes designed and built, Currently, this cenit can handle voltage up to 23 KV with a voltage drop to zen tc below 0.2 ms, The schematic of the circuit is shown in figure 7 and this cincuil will be improved in the near Furuse 50 that higher vollage (10 kV) cin be upplied inthe Figure 7. measarement, We are also in ee piocess of dasigaing ond huilting a circuit with high voltage ant high speed capability using GBT switch us measuce the discharged energy densicy released Usa resisive lord, Using the circuit of Agere 7, the discharge encrgy density for the terpolymers was characterizet, In thie measurements, the failing time af the voltage pul is adjusted tn 1 ans and the aetual-maeanuring time is 1.25 ms, The results from these discharge measurements ure summarized in Tables 4 (Zor che low fiatds) and ‘Tables 5 aad ffor the high felis) for the Uerpolyrmer of 70/30/81 TSL17) and 68/37/7.5 mol (SL14). Tile 4 en ee Serake os fol Oie) Grey ite) FlpTibes | etede Oi 18.-17, sulion casting + unowetohéel (7008.4 mos 1084 212 2tyr 245 mm TS.-17, colton casting __sHtelthed £70306.1 mat 4aze 23b 16 2p ISL-14 solution casing Unetsiched (B9/S277 5 ae) ja07 269216 as “The highest fekls measured for these ims wore limited by the cru: voltage 2.3 2V}. The dat indicate abut wih abouc | ms discharge time and under 320 MVim, hese terpoy films ean reach energy deesity higher dhan 6.6 Mem. rom the energy densi daia ound from the unipolar polerzavon Toop, itis expected that with ncrensed Fel, this energy density wil be increased, Tor example, gue 6 shows that forthe terpolymer 68/3777. iol under 320 MVim, the discharged enerey densi measured a 10 (LGD ms 8m he tangs fom 47 Hor 08 en? Tie data in Table 3 (gure 8) show thls 32 NV, he Gog energy esis forthe sate erpolyiner measured st 1 ms is 6.64 Tea? sshich is tou yor ach below dat fro gure 6 “Table 4. Discharge Energy uf TSI.-14 (6837/7.5 mal Filen on Glass Substrate 1 Blectrie field Releaiod Eoergy —‘Fallingtime | Film Thickness (MVim} ion?) ¢ans), (urn) ST O5a6 125 ie1__[ 1.606 135 i 178 B02 125, _ 286 atte 135 2855 S55 135 wld 837 igs. ‘Table 6. Discharge Energy of ISL-17 (70/30/81 ul) Film an Glass Substrate Electric field ‘Released Entre) 7 Falling time [Thickness ova em) . (um) Ea 08 i Ee [ 700 19% 125 8 1 3.366 [125 3 200 Aaa [438 # 225 a ee a 250 S12 [ise The discharge tha forthe terpolymer 65/35/8.6 (SLE) was haraerized ot room tomperatres ane SO °C aul at two sischarging toe ane tas time, 128 ms ond O64 ms. ‘The data are summarized jo Tables 7. § and 9. ‘There is not large difference ir the discharged enerey density between that measured vith 128 ms discharge time and 0.64 ms discharge time (also see figure 9}, Haims of two different an - thicknesses were tested: 3.6. yon Etunviny and 11 jim and the data seem to Tigone 8 indicate that the encrgy densicy of 3.6 jm thick films undor same electric fic is lower than that of 11 yim fick, Forthor tests will be performed fo confirm this, ‘hore is no marked difference inthe cnrgy density between that measured at room temperature (20 °C} and that at $0°°C under the sams field. Howver, the breskdowe fiold of the films at 50 Cis lower which might be due to the reduced chstic modulos of the terpolyer film with comperatare {oleckromechanical breakdown). Further investigation will br performed oe En ‘Table 7 Discharge duln for l-5 (65/35/8,6% thigknes Hr) al room temperature Blcctric | Discharge Discharge | Thickness | Diameter soe | Beek | time (mss | em) | tm) (Mvfm) (feo) - 1 ato | 19838) 2a 3 bat [abe 36 346 095 | 838 246 13H W321i a 1.28 3.6 2.46 147 | 206] hs 38 2.46 a ee 3A | 246 217 3.45 1.28 3.8 | 246 5 is is 258 4d 128 36 2.46 2 our | 6 36 26 59 oa? [aus 3B 26 os | _ost 36 26 ast [uz 1a?_[ 064 36 2 152 199 [046 35 Bah ist [273 | 06 35 246 ase 373] “ose 35 2