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Sodium a tam tuk caah, sodium-ion battery (NIBs) nih electrochemical thazaang chiahnak caah ruahchannak a ummi lam dang a aiawh. Atu lio ah, NIB thiamnak tthanchonak ah a biapi bikmi dawnkhantu cu caan saupi chung sodium ions pawl kha a kirter khomi electrode thilri a um lo caah a si. Cucaah, hi hlathlainak nih aa tinhmi cu NIB electrode thilri ah polyvinyl alcohol (PVA) le sodium alginate (NaAlg) cawhmi cung ah glycerol chapnak nih a chuahpimi thil kha theory lei in hlathlai ding a si. Hi hlathlainak nih hin PVA, sodium alginate, le glycerol cawhmi cung ah hram bunhmi polymer electrolytes hna i electronic, thermal, le quantitative structure-activity pehtlaihnak (QSAR) fianternak hna kha a biapi in a chiah. Hi thilri hna hi semi-empirical lam le density functional theory (DFT) hmangin hlathlainak an tuah hna. A sining hlathlainak nih PVA/alginate le glycerol karlak pehtlaihnak konglam a langhter caah, band gap thazaang (Eg) kha hlathlainak tuah a si. A phichuak nih a langhter mi cu glycerol chapnak nih Eg man kha 0.2814 eV tiang a zorter. Molecular electrostatic potential surface (MESP) nih electron-a tammi le electron-a tlawmmi hmun le molecule charges hna i an i phawtzamhnak kha electrolyte system dihlak ah a langhter. Hlathlainak tuahmi lumnak tahfung hna cu enthalpy (H), entropy (ΔS), lumnak tthawnnak (Cp), Gibbs zalong thazaang (G) le sernak lumnak hna an si. Cun, hi hlathlainak ah hin quantitative structure-activity pehtlaihnak (QSAR) descriptors zeimawzat, cu hna cu total dipole moment (TDM), total energy (E), ionization potential (IP), Log P le polarizability tibantuk hna kha an hlathlai. A phichuak nih a langhter mi cu H, ΔS, Cp, G le TDM cu lum le glycerol dat a karh tikah an karh. Cu lio ah, sernak lumnak, IP le E a zor, cu nih cun a lehrulhnak le a tthencheunak a tthanchoter. Cun, glycerol chapnak thawngin, cell voltage cu 2.488 V tiang a karh. DFT le PM6 tuaktannak hna cu a man a fawimi PVA/Na Alg glycerol-based electrolytes cung ah hram bunh in a langhter mi cu an riantuannak tampi ruangah lithium-ion battery pawl kha tlawmpal in an thlen khawh hna, asinain tthanchonak le hlathlainak tuah chap a herh rih.
Lithium-ion battery (LIBs) cu mi tampi nih an hman ko nain, an hmannak nih a tawimi nunnak, a man a fakmi le himnak kong lungretheihnak ruangah rikhiahnak tampi a tong. Sodium-ion battery (SIBs) cu LIBs caah hman khawhmi lam dang ah an cang kho, zeicahtiah an tam tuk, an man a fawi, cun sodium element a fahter lo. Sodium-ion battery (SIBs) cu electrochemical thilri caah a biapi chin lengmangmi thazaang chiahnak system ah an cang1. Sodium-ion battery pawl cu ion kalnak le electric current chuahternak caah electrolytes cungah tampi an i hngatchan2,3. Liquid electrolytes cu a bik in thir chiti le organic solvents in sermi an si. Hman khawhnak ding caah ti electrolytes himnak kong kha ralring tein ruah a hau, a hlei in battery cu lumternak asiloah electric nih a den tikah4.
Sodium-ion battery (SIBs) nih rili chung thilri tampi an ngeih caah, a ttha lomi le thilri man a tlawm caah hmailei caan rau lo te ah lithium-ion battery aiawh an si lai tiah ruah a si. Nanomaterials sernak nih data chiahnak, electronic, le optical thilri sernak a rangter. Cauk tampi nih sodium-ion battery ah nanostructures phunphun (tahchunhnak ah, thir oxides, graphene, nanotubes, le fullerenes) hmannak kong an langhter. Hlathlainak nih cun sodium-ion battery caah polymer telh in anode thilri sernak ah a biapi in a chiah, zeicahtiah an hman khawhnak le pawngkam caah a ttha. Recharge khawhmi polymer battery kong he pehtlai in hlathlainak tuah duhnak cu lunghrin awk um loin a karh lai. A dang tein a ummi sining le sining a ngeimi polymer electrode thilri thar hna nih pawngkam he aa remmi thazaang chiahnak thiamnak caah lam a hun lai. Sodium-ion battery ah hman ding in polymer electrode thilri phunphun an kawl ko nain, hi rian hi a hramthawknak ah a um rih. Sodium-ion battery caah, a sining aa dangmi polymer thilri tam deuh kawl a herh. Polymer electrode thilri chung i sodium ions chiahnak lam kong kan theihmi cungah hram bunh in, aa pehtlaimi system chung i carbonyl phu, free radicals le heteroatoms hna cu sodium ions he pehtlaihnak caah a cawlcangmi hmun ah an hman khawh tiah ruahnak cheuh khawh a si. Cucaah, hi a cawlcangmi hmun hna i an tamnak a sangmi polymer thar ser cu a biapi tuk. Gel polymer electrolyte (GPE) cu battery zumhawktlak sinak, ion hruai khawhnak, a luang lonak, a nemnak sang, le riantuan ning ttha a tthanchotertu thiamnak dang pakhat a si12.
Polymer matrices ah PVA le polyethylene oxide (PEO)13 tibantuk thilri hna an i tel. Gel permeable polymer (GPE) nih polymer matrix chung i ti electrolyte kha a cawl kho lo, cu nih cun chawlehnak ah hmanmi tthennak he tahchunh tikah a luan khawhnak a zorter14. PVA cu sermi thilnung in a rawk khomi polymer a si. Permittivity sang a ngei, a man a fawi i a thurhnawm lo. Mah thilri cu a zukcawl ser khawhnak, chemical fek tein um khawhnak le aa hngat khawhnak caah theih a si. Cun riantuan khawhnak (OH) phu le a sangmi aa pehtlaimi thil ti khawhnak a ngei15,16,17. Polymer cawhnak, plasticizer chapnak, fonhmi chapnak le in situ polymerization thiamnak hna cu PVA-based polymer electrolytes hna i an hruai khawhnak tthanchoternak caah matrix crystallinity zorternak le chain flexibility karhternak caah hman an si18,19,20.
Cawhnak cu riantuannak caah hmanmi polymeric thilri sernak caah a biapi mi lam pakhat a si. Polymer cawhmi hna cu a tanglei ah hman a si tawn: (1) riantuannak ah hmanmi thilnung polymer hna riantuan ning tthanchoter; (2) a rawk khomi thilri hna i chemical, physical le mechanical sining hna kha tthanchoter; le (3) rawl chiahnak riantuannak ah thilri thar herhnak aa thleng lengmangmi he aa tlak in i remh. Copolymerization he aa lo loin, polymer cawhnak cu a man a fawimi thil tuahnak a si i duhmi thilri hmuh khawhnak ding caah a harmi chemical thil sining nakin a sawhsawh mi thilri thil sining a hman21. Homopolymers ser awkah, polymers phunphun nih dipole-dipole thazaang, hydrogen pehtlaihnak, asiloah charge-transfer complexes hmangin an i pehtlaih khawh22,23. Thilnung le sermi polymers in sermi cawhmi nih hin a ttha ngaimi nunnak he aa tlaknak le a ttha ngaimi thilri sining hna kha a fonh khawh, cu nih cun thilchuah man tlawmte in a ttha deuhmi thilri a ser khawh24,25. Cucaah, sermi le sermi polymer pawl cawh in biorelevant polymeric thilri sernak ah lungthawhnak nganpi a um. PVA cu sodium alginate (NaAlg), cellulose, chitosan le starch26 he fonh khawh a si.
Sodium alginate cu rili chung i a senmi thingram chungin chuahmi a chuakmi polymer le anionic polysaccharide a si. Sodium alginate cu β-(1-4)-linked D-mannuronic acid (M) le α-(1-4)-linked L-guluronic acid (G) hna cu homopolymeric phun (poly-M le poly-G) le heteropolymeric blocks (MG or GM)27 ah an i tthen. M le G block chung i a ummi le aa pehtlaimi zat nih alginate chemical le physical sining cungah tampi huham a ngei28,29. Sodium alginate cu a rawk khawhnak, a nunnak he aa tlak khawhnak, a man a fawi, a ttha mi zukcawl ser khawhnak le a ttha lo caah mi tampi nih an hman i hlathlainak an tuah. Sihmanhsehlaw, alginate hri chung i free hydroxyl (OH) le carboxylate (COO) phu tampi nih alginate cu ti a duh tukmi ah a ser. Sihmanhsehlaw, alginate cu a nemmi le a fekmi a si caah a ttha lomi thilri sining a ngei. Cucaah, alginate cu a dang sermi thilri hna he fonh in ti theih khawhnak le riantuan ning tthanchoter khawh a si30,31.
Electrode thilri thar suai hlanah, thilri thar ser khawhnak tuaktannak caah DFT tuaktannak kha hman a si tawn. Cun, scientist pawl nih hneksaknak hmuhmi fehternak le chimchungnak caah molecular modeling an hman, caan an khon, chemical hlohmi an zorter, cun pehtlaihnak ziaza an chimchung32. Molecular modeling cu thilri science, nanomaterials, computational chemistry, le sii hmuhchuahnak tibantuk rian tampi ah a tthawngmi le a biapi mi science zung pakhat ah a cang33,34. Model tuahnak program hmangin, scientist pawl nih direct in molecular data an hmuh khawh, cu ah cun thazaang (sernak lumnak, ionization potential, activation thazaang, tbk.) le geometry (bond angles, bond lengths, le torsion angles)35 aa tel. Cun, electronic sining (charge, HOMO le LUMO band gap energy, electron affinity), spectral sining (FTIR spectra tibantuk sining langhternak hninhnak phun le thazaang), le bulk sining (volume, diffusion, viscosity, modulus, tbk.)36 tuak khawh a si.
LiNiPO4 nih a thazaang tthawnnak (riantuannak voltage 5.1 V hrawng) ruangah lithium-ion battery positive electrode thilri hna he i zuamnak ah tthatnak a langhter. LiNiPO4 nih a chuahpimi ṭhatnak kha a sangmi voltage hmun ah tling tein hman khawh awkah, rianṭuannak voltage kha tlawmter a hau, zeicahtiah atu lio sermi a sangmi voltage electrolyte cu 4.8 V tang voltage ah a tlawmpal lawng a fekmi a si kho. Zhang et al. LiNiPO4 i Ni hmun ah 3d, 4d, le 5d thlennak thir vialte hna i an i fonhnak kong an hlathlai, a ttha tukmi electrochemical riantuannak he i fonhnak pattern pawl kha an thim hna, cun LiNiPO4 riantuannak voltage kha a remh i a electrochemical riantuannak i aa pehtlaimi fekmi kha an kilven. An hmuhmi riantuannak voltage niam bik cu Ti, Nb, le Ta-doped LiNiPO4 caah 4.21, 3.76, le 3.5037 an si.
Cucaah, hi hlathlainak nih aa tinhmi cu, ion-ion battery ah hmannak caah quantum mechanical tuaktannak hmangin PVA/NaAlg system i electronic thilri, QSAR fianternak le lumnak thilri cung ah plasticizer pakhat a simi glycerol nih a chuahpimi thil kha theory lei in hlathlai ding a si. PVA/NaAlg model le glycerol karlak i molecule pehtlaihnak cu Bader's quantum atomic theory of molecules (QTAIM) hmangin hlathlainak tuah a si.
PVA le NaAlg le cu hnu ah glycerol he pehtlaihnak a langhtermi molecule model cu DFT hmangin a ttha bik in ser a si. Model cu Gaussian 0938 software hmangin Spectroscopy Department, National Research Center, Cairo, Egypt ah tuak a si. Model pawl cu B3LYP/6-311G(d, p) level39,40,41,42 ah DFT hmangin an remh hna. Hlathlainak tuahmi model hna karlak pehtlaihnak fehternak caah, theory tlukruannak ah tuahmi frequency hlathlainak nih a ttha bikmi geometry a fekmi a langhter. Hlathlainak tuahmi frequency vialte lakah a ttha lomi frequency a um lonak nih a si khomi thazaang cunglei ah a dikmi positive minima ah ruahmi sining kha a langhter. TDM, HOMO/LUMO band gap energy le MESP tibantuk taksa lei thilri hna cu theory quantum mechanical tlukruannak ah an tuak. Cun, a donghnak lumnak sernak, zalongmi thazaang, entropy, enthalpy le lumnak tthawnnak tibantuk lumnak tahfung cheukhat cu Table 1 ah pekmi formula hmangin tuak an si. Hlathlainak tuahmi model hna cu hlathlainak tuahmi thilri hna cung i a cangmi pehtlaihnak hna hngalh khawhnak ding caah molecule chung i atom hna i quantum theory (QTAIM) hlathlainak ah an chiah hna. Hi tuaktannak hna cu Gaussian 09 software code chung i “output=wfn” nawlpeknak hmangin tuah a si i Avogadro software code43 hmangin hmuh khawh a si.
E cu chunglei thazaang a si, P cu hneknak a si, V cu a ngan ning a si, Q cu system le a pawngkam karlak i lumnak i thlennak a si, T cu lumnak a si, ΔH cu enthalpy thlennak a si, ΔG cu zalongmi thazaang thlennak a si, ΔS cu entropy thlennak a si, a le b cu hninhnonak tahfung a si, q cu atom charge a si, cun C cu atomic electronity a si, 45445. A donghnak ah, aa khatmi sining hna cu an remh i QSAR parameters cu PM6 level ah SCIGRESS software code46 hmangin Cairo, Egypt um National Research Center i Spectroscopy Department ah an tuak.
Kan riantuannak hlan47 ah, PVA unit pathum le NaAlg unit pahnih an i pehtlaihnak a langhtermi a si kho bikmi model kha kan zohfel, glycerol nih plasticizer rian a ttuan. A cunglei ah kan chim cang bantuk in, PVA le NaAlg i pehtlaihnak caah lam pahnih a um. Model pahnih, 3PVA-2Na Alg (carbon nambar 10 cung ah hram bunh in) le Term 1Na Alg-3PVA-Mid 1Na Alg tiah min an sakmi hna cu, a dang ruahmi sining hna he tahchunh tikah a hme bikmi thazaang tthencheunak man48 an ngei. Cucaah, PVA/Na Alg cawhmi polymer i a si kho bikmi model cung i Gly chapnak nih a chuahpimi thil cu a hnu bik sining pahnih hmangin hlathlainak tuah a si: 3PVA-(C10)2Na Alg (a fawinak caah 3PVA-2Na Alg tiah auhmi) le Term 1 Na Alg − 3PVA-Mid 1 Na Alg. Cauk ning in, PVA, NaAlg le glycerol nih hydroxyl riantuannak phu karlak ah a derthawmmi hydrogen pehtlaihnak lawng an ser khawh. PVA trimer le NaAlg le glycerol dimer pahnih nih OH phu zeimawzat an ngeih caah, pehtlaihnak cu OH phu pakhat hmangin tuah khawh a si. Figure 1 nih model molecule le model molecule 3PVA-2Na Alg karlak pehtlaihnak a langhter, cun Figure 2 nih model molecule Term 1Na Alg-3PVA-Mid 1Na Alg le glycerol tlawmtam aa dangmi karlak pehtlaihnak sermi model a langhter.
A ttha bikmi sining: (a) Gly le 3PVA − 2Na Alg nih (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, le (f) 5 Gly he an i pehtlaih.
Term 1Na Alg- 3PVA –Mid 1Na Alg (a) 1 Gly, (b) 2 Gly, (c) 3 Gly, (d) 4 Gly, (e) 5 Gly, le (f) 6 Gly he pehtlaihnak a ngeimi Term 1Na Alg- 3PVA –Mid 1Na Alg i a ttha bikmi sining hna.
Electron band gap thazaang cu zeibantuk electrode thilri hmanh a tthatnak kong hlathlainak tuah tikah ruah awk a biapi mi thil pakhat a si. Zeicatiah thilri cu lenglei thlennak a tong tikah electron pawl an umtuning kha a langhter. Cucaah, hlathlainak tuahmi sining vialte caah HOMO/LUMO i electron band gap thazaang hna kha tuaktan a herh. Table 2 nih 3PVA-(C10)2Na Alg le Term 1Na Alg − 3PVA- Mid 1Na Alg i HOMO/LUMO thazaang thlennak kha glycerol chapnak ruangah a langhter. Ref47 ning in, 3PVA-(C10)2Na Alg i Eg man cu 0.2908 eV a si, cu lio ah a pahnihnak pehtlaihnak (cucu, Term 1Na Alg − 3PVA- Mid 1Na Alg) a si khomi a langhtermi sining i Eg man cu 0.5706 eV a si.
Sihmanhsehlaw, glycerol chapnak nih 3PVA-(C10)2Na Alg Eg man tlawmpal a thlen ti hmuh a si. 3PVA-(C10)2NaAlg nih 1, 2, 3, 4 le 5 glycerol units he pehtlaihnak a tuah tikah, a Eg man cu 0.302, 0.299, 0.308, 0.289 le 0.281 eV ah an cang. Sihmanhsehlaw, glycerol unit 3 chap hnu ah, Eg man cu 3PVA-(C10)2Na Alg nakin a hme deuh timi man a ngeimi hmuhnak a um. 3PVA-(C10)2Na Alg le glycerol unit panga pehtlaihnak a langhtermi model cu a si kho bikmi pehtlaihnak model a si. A sullam cu glycerol unit a karh tikah, pehtlaihnak a um khawhnak zong a karh ve tinak a si.
Cu lio ah, pehtlaihnak a si khomi pahnihnak caah, Term 1Na Alg − 3PVA –Mid 1Na Alg- 1Gly, Term 1Na Alg − 3PVA –Mid 1Na Alg- 2Gly, Term 1Na Alg − 3Na Alg- 1Gly, Term 1Na Alg- 3PVA – 3PVA – 3PVA – 3PVA Alg- Na Algly a aiawhmi model molecule hna i HOMO/LUMO thazaang hna Alg − 3PVA –Mid 1Na Alg- 4Gly, Term 1Na Alg − 3PVA –Mid 1Na Alg- 5Gly le Term 1Na Alg − 3PVA –Mid 1Na Alg- 6Gly cu 1.343, 1.34 7, 0.976, 0.607, 0.67, 0.046, 696 ah an cang. pakhat hnu pakhat. Table 2 nih hin thilri vialte caah tuakmi HOMO/LUMO band gap thazaang kha a langhter. Cun, a hmasa bik phu i pehtlaihnak a si khomi ziaza aa khatmi kha hika ah hin a langhter tthan.
Solid state physics ah band theory nih cun electrode thilri i band gap a zor tikah, thilri i electronic conductivity a karh tiah a ti. Sodium-ion cathode thilri hna i an band gap zorternak caah doping cu a tlangpi in hmanmi lam pakhat a si. Jiang le a dangdang. β-NaMnO2 tthencheu thilri hna i electronic hruainak tthanchoter awkah Cu doping hman. DFT tuaktannak hmangin, doping nih thilri band gap kha 0.7 eV in 0.3 eV tiang a zorter ti kha an hmuh. Cu nih hin Cu doping nih β-NaMnO2 thilri electronic hruainak a tthanchoter ti a langhter.
MESP cu molecule charge phawtzamhnak le a ttha mi charge pakhat karlak i pehtlaihnak thazaang tiah fianter a si. MESP cu chemical sining le thlennak hngalhthiamnak le fianternak caah thilri ttha pakhat ah ruah a si. MESP cu polymeric thilri karlak pehtlaihnak kalning hngalhthiamnak caah hman khawh a si. MESP nih hlathlainak tuahmi compound chung i charge phawtzamhnak kha a langhter. Cun, MESP nih hlathlainak tuahmi thilri chung i a cawlcangmi hmun hna kong thawngpang a pek32. Figure 3 nih MESP plot pawl kha a langhter 3PVA-(C10) 2Na Alg − 5Gly cu B3LYP/6-311G(d, p) theory level ah a chimchung.
(a) Gly le 3PVA − 2Na Alg (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, le (f) 5 Gly he pehtlaihnak caah B3LYP/6-311 g(d, p) in tuakmi MESP contour hna.
Cu lio ah, Fig. 4 nih Term 1Na Alg- 3PVA – Mid 1Na Alg, Term 1Na Alg-3PVA – Mid 1Na Alg- 1Gly, Term 1Na Alg-3PVA – Mid 1Na Alg − 2Gly, Term 1Na Alg-3PVA – PVA – Mid 1Gly, Term 1Na Alg-3PVA caah MESP tuakmi a phichuak a langhter Term 1Na Alg-3PVA – Mid 1Na Alg − 4Gly, Term 1Na Alg- 3PVA – Mid 1Na Alg- 5gly le Term 1Na Alg-3PVA – Mid 1Na Alg − 6Gly, ciocio. Tuakmi MESP cu contour ziaza in langhter a si. Contour line pawl cu rong phunphun in langhter an si. Rong pakhat cio nih aa dangmi electronegativity man a aiawh. A senmi rong nih hin electronegative asiloah a tthawngmi hmun pawl kha a langhter. Cu lio ah, a senmi rong nih cun innchungkhar chung i a tlarimi hmun 49, 50, 51 kha a aiawh. MESP hmuhmi nih a langhter mi cu 3PVA-(C10)2Na Alg i a riantuan khawhnak cu hlathlainak tuahmi model pawngkam ah a senmi rong a karh tikah a karh. Cu lio ah, Term 1Na Alg-3PVA – Mid 1Na Alg model molecule i MESP map chung i a senmi rong a tthawnnak cu glycerol aa dangmi he pehtlaihnak ruangah a zor. Ruahchannak pekmi sining pawngkam ah a senmi rong tthencheunak thlennak nih a tthawntermi a langhter, cu lio ah a tthawngmi a karhmi nih glycerol dat a karhmi ruangah 3PVA-(C10)2Na Alg model molecule i electronegativity a karhmi kha a fehter.
B3LYP/6-311 g(d, p) tuakmi MESP Term 1Na Alg-3PVA-Mid 1Na Alg nih (a) 1 Gly, (b) 2 Gly, (c) 3 Gly, (d) 4 Gly, (e) 5 Gly, le (f) 6 Gly he pehtlaihnak a tuah.
A chuahpimi thilri vialte nih 200 K in 500 K karlak ah a dangdang lumnak ah tuakmi enthalpy, entropy, lumnak tthawnnak, zalong tein thazaang le sernak lumnak tibantuk an lumnak tahfung hna an ngei. Physical system hna an ziaza fianternak caah, an electronic ziaza hlathlainak lengah, an lumnak ziaza zong an lumnak ziaza kha hlathlai a herh, cucu pakhat le pakhat an i pehtlaihnak ruangah a si kho Table 1 ah pekmi equation hmangin tuakmi a si. Hi lumnak tahfung hna hlathlainak cu lumnak aa dangmi ah cu bantuk thilri hna i an lehrulhnak le an fekmi a langhtertu a biapi mi ah ruah a si.
PVA trimer enthalpy kongah, a hmasa bik ah NaAlg dimer he aa pehtlaih, cun carbon atom #10 he aa pehtlaimi OH phu hmangin, cun a donghnak ah glycerol he aa pehtlaih. Enthalpy cu thermodynamic system chung i thazaang tahnak a si. Enthalpy cu system chung i lumnak dihlak he aa tluk, cucu system chung thazaang he aa tluk i a ngan le a hmetnak he aa tluk. Phundang in chim ahcun, enthalpy nih thil pakhatkhat ah zeitluk in dah lumnak le rian an chap asiloah an chuah timi a langhter52.
Figure 5 nih 3PVA-(C10)2Na Alg le glycerol tlawmtam aa dangmi an i pehtlaih lio ah enthalpy thlennak a langhter. A0, A1, A2, A3, A4, le A5 timi biafang tawite hna nih model molecule 3PVA-(C10)2Na Alg, 3PVA-(C10)2Na Alg − 1 Gly, 3PVA-(C10)2Na Alg − 2Gly, 3PVA-(C10)2Na Alg − 3Gly, 3PVA-(C10)2Na Alg − 4Gly, le 3PVA-(C10)2Na Alg − 5Gly, ciocio. Figure 5a nih a langhter mi cu lumnak le glycerol dat a karh tikah enthalpy a karh. 200 K ah 3PVA-(C10)2NaAlg − 5Gly (ie, A5) aiawhtu sining enthalpy cu 27.966 cal/mol a si, cu lio ah 200 K ah 3PVA- 2NaAlg aiawhtu sining enthalpy cu 13.490 cal/mol a si. A donghnak ah, enthalpy cu a ttha caah, hi lehrulhnak cu endothermic a si.
Entropy cu kharmi thermodynamic system chung i hmuh khawh lomi thazaang tahnak tiah fianter a si i system a ttha lonak tahnak ah ruah a si tawn. Figure 5b nih 3PVA-(C10)2NaAlg lumnak he aa pehtlaimi entropy thlennak le glycerol unit phunphun he zeitindah aa pehtlaih timi a langhter. Graph nih a langhter mi cu 200 K in 500 K tiang lumnak a karh tikah entropy cu a tlarimi in aa thleng. Figure 5b nih fiang tein a langhter mi cu 3PVA-(C10)2Na Alg model i entropy cu 200 K ah 200 cal/K/mol ah a kal, zeicahtiah 3PVA-(C10)2Na Alg model nih lattice a langhter lo. Lungthawhnak a karh tikah, 3PVA-(C10)2Na Alg model cu a buai i lumnak a karh tikah entropy a karh ning a fianter. Cun, 3PVA-C10 2Na Alg- 5 Gly dirhmun nih entropy man a sang bik a ngeih ti cu a fiang ko.
Cu bantuk ziaza cu hmanthlak 5c ah hmuh khawh a si, mah nih cun lumnak he aa pehtlaimi lumnak thazaang thlennak a langhter. Lungthawhnak tthawnnak cu thil pakhatkhat lumnak kha 1 °C47 in thlen awkah a herhmi lumnak zat kha a si. Figure 5c nih 1, 2, 3, 4, le 5 glycerol units he pehtlaihnak ruangah model molecule 3PVA-(C10)2NaAlg lumnak thazaang thlennak a langhter. Hmanthlak nih a langhter mi cu model 3PVA-(C10)2NaAlg lumnak thazaang cu lumnak he aa tlaiin a karh. Lungthawhnak a karh tikah hmuhmi lumnak thazaang a karhmi cu phonon lumnak hninhnak ruangah a si. Cun, glycerol dat karhternak nih model 3PVA-(C10)2NaAlg lumternak thazaang a karhter timi tehte a um. Cun, a sining nih a langhter mi cu 3PVA-(C10)2NaAlg−5Gly cu a dang sining he tahchunh tikah a sang bikmi lumternak man a ngei.
A dang parameters hna cu free energy le a donghnak lumnak tibantuk hna cu hlathlainak tuahmi thilri hna caah tuak an si i Figure 5d le e ah an langhter hna. A donghnak lumnak cu a thiangmi thil pakhatkhat kha a chung thilri hna in a zungzal in hneknak tangah a chuah lio ah a chuakmi asiloah a lakmi lumnak a si. Zalongmi thazaang cu thazaang he aa lo mi thilri tiah fianter khawh a si, cucu, a man cu thermodynamic dirhmun pakhat cio ah thilri zat cungah aa hngat. 3PVA-(C10)2NaAlg−5Gly sernak thazaang le lumnak cu a niam bik a si i -1318.338 le -1628.154 kcal/mol an si. Cu he aa dang in, 3PVA-(C10)2NaAlg aiawhtu sining nih a dang sining he tahchunh tikah -690.340 le -830.673 kcal/mol tluk in zalong tein thazaang le sernak lumnak a sang bik a ngei. Figure 5 ah hmuh khawhmi bantuk in, glycerol he pehtlaihnak ruangah lumnak sining phunphun an i thleng. Gibbs free energy cu a ttha lo, cu nih cun ruahnak cheuhnak sining cu a fekmi a si ti a langhter.
PM6 nih a thiangmi 3PVA- (C10) 2Na Alg (model A0), 3PVA- (C10) 2Na Alg − 1 Gly (model A1), 3PVA- (C10) 2Na Alg − 2 Gly (model A2), 3PVA- (C10) 2 Gly (model A2), 3PVA- (C10) 33-Gly (3PVA-Gly) hna i lumnak tahfung kha a tuak (C10) 2Na Alg − 4 Gly (model A4), le 3PVA- (C10) 2Na Alg − 5 Gly (model A5), cuka ahcun (a) cu enthalpy a si, (b) entropy, (c) lumnak thazaang, (d) zalongmi thazaang, le (e) sernak lumnak a si.
Khatlei kam in, PVA trimer le dimeric NaAlg karlak i pehtlaihnak phun hnihnak cu PVA trimer sining ah a donghnak le a laifang OH phu ah a cang. Pakhatnak phu bantuk in, lumnak tahfung hna cu theory tlukruannak hmangin tuak an si. Figure 6a-e nih enthalpy, entropy, lumnak tthawnnak, zalongmi thazaang le, a donghnak ah, sernak lumnak aa dangmi a langhter. Term 1 NaAlg-3PVA-Mid 1 NaAlg i enthalpy, entropy le lumternak nih 1, 2, 3, 4, 5 le 6 glycerol units he pehtlaihnak an tuah tikah a hmasa bik phu he aa khatmi ziaza an langhter ti kha hmanthlak 6a-c nih a langhter. Cun, an man cu lumnak a karh tikah zaangfah tein a karh. Cun, ruahnak cheuhnak Term 1 Na Alg − 3PVA-Mid 1 Na Alg model ah, enthalpy, entropy le lumternak man cu glycerol dat a karh tikah a karh. B0, B1, B2, B3, B4, B5 le B6 timi biafang tawite hna nih a tanglei sining hna kha an aiawh: Term 1 Na Alg − 3PVA- Mid 1 Na Alg, Term 1 Na Alg- 3PVA- Mid 1 Na Alg − 1 Gly, Term 1 Na Alg- 3PVA- Mid Alg- Na Alg- 2 Alg- 2 Alg- 1 3PVA- Mid 1 Na Alg − 3gly, Term 1 Na Alg- 3PVA- Mid 1 Na Alg − 4 Gly, Term 1 Na Alg- 3PVA- Mid 1 Na Alg − 5 Gly le Term 1 Na Alg- 3PVA- Mid 1 Na Alg − 6 Gly. Fig. 6a-c ah hmuh khawhmi bantukin, glycerol unit zat 1 in 6 tiang a karh tikah enthalpy, entropy le lumternak man cu a karh ti cu a fiang ko.
PM6 nih a thiangmi Term 1 Na Alg- 3PVA- Mid 1 Na Alg (model B0), Term 1 Na Alg- 3PVA- Mid 1 Na Alg – 1 Gly (model B1), Term 1 Na Alg- 3PVA- Mid 1 Na Alg – 2 Gly (model PVA-Mid 1 Na Alg – 2 Gly), Term PVA-Mid 11 Na Alg – 3 Gly (model B3), Term 1 Na Alg- 3PVA- Mid 1 Na Alg – 4 Gly (model B4), Term 1 Na Alg- 3PVA- Mid 1 Na Alg – 5 Gly (model B5), le Term 1 Na Alg- 3PVA- Mid 1 Na Alg – 6 Gly (model B3) telh in (b), entropy, (c) lum khawhnak, (d) zalongmi thazaang, le (e) sernak lumnak.
Cun, Term 1 Na Alg- 3PVA- Mid 1 Na Alg- 6 Gly aiawhtu sining cu a dang sining he tahchunh tikah enthalpy, entropy le lumternak man a sang bik a ngei. Cu hna lakah, an man cu Term 1 Na Alg − 3PVA- Mid 1 Na Alg ah 16.703 cal/mol, 257.990 cal/mol/K le 131.323 kcal/mol in 33.223 cal/mol, 420.038 cal/mol/mol/mol/mol le 52323 kcal/mol tiang a kai. Term 1 ah Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly, ciocio.
Sihmanhsehlaw, hmanthlak 6d le e nih zalongmi thazaang le a donghnak lumnak (HF) i lumternak hngatchannak kha a langhter. HF cu thil pakhatkhat mole pakhat cu a sining le a tlarimi thil sining tangah a thilri hna in a chuah tikah a cangmi enthalpy thlennak tiah fianter khawh a si. Hmanthlak chungin a fiangmi cu, hlathlainak tuahmi thilri vialte hna i an zalongmi thazaang le a donghnak lumnak nih lumnak cungah aa hngatmi a langhter, cucu, lumnak a karh tikah zaangfah tein le a tlarimi in an karh. Cun, hmanthlak nih Term 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly aiawhtu sining nih a niam bikmi zalongmi thazaang le a niam bikmi HF a ngei ti zong a fehter. Parameter pahnih cu -758.337 in -899.741 K cal/mol tiang 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly ah -1,476.591 le -1,828.523 K cal/mol tiang an zor. A phichuak in a fiangmi cu HF cu glycerol unit a karh tikah a zor. A sullam cu riantuannak phu an karh caah, lehrulhnak zong a karh i cucaah lehrulhnak tuah awkah thazaang tlawm deuh a herh tinak a si. Mah nih hin plasticized PVA/NaAlg cu a tthawn tuk caah battery ah hman khawh a si ti a fehter.
A tlangpi in, lumnak nih a chuahpimi thil hna cu phun hnih in an ṭhen hna: lumnak niam nih a chuahpimi thil le lumnak sang nih a chuahtermi thil. Khuacaan niam nih a chuahpimi thil cu Greenland, Canada le Russia tibantuk hmun sang ah a ummi ram hna ah a bik in theih khawh a si. Khuasik caan ah, hi hmun hna i lenglei thli lumnak cu zero degree Celsius tang ah a um. Lithium-ion battery hna an nunchung le an riantuan ning cu a niammi lumnak nih a hnorsuan khawh, a hlei in plug-in hybrid electric mawtaw, electric mawtaw thiang, le hybrid electric mawtaw ah hmanmi hna. Vancung khualtlawnnak cu lithium-ion battery a herhmi a kikmi pawngkam dang pakhat a si. Tahchunhnak ah, Mars cung lumnak cu -120 degree Celsius tiang a tla kho, cu nih cun vanlawng ah lithium-ion battery hmannak ah dawnkhantu nganpi a chuahter. Riantuannak lumnak a niam ahcun lithium-ion battery hna i an charge thlennak rate le chemical reaction cawlcanghnak a zorter khawh, cu nih cun electrode chung i lithium ions i a karhnak rate le electrolyte chung i ionic conductivity a zorter khawh. Hi rawhnak nih hin thazaang chuah khawhnak le thazaang a zorter, cun a caan ahcun riantuan ning zong a zorter53.
A sangmi lumnak nih a chuahpimi thil cu hmannak pawngkam phunphun ah a cang, a sangmi le a niammi pawngkam hna zong aa tel, cun a niammi lumnak nih a chuahtermi cu a niammi hmannak pawngkam ah a tlawm deuh. A tlawmmi lumnak nih a bik in pawngkam lumnak nih a khiah, cu lio ah lumnak sang nih a chuahpimi cu riantuan lio ah lithium-ion battery chung i a sangmi lumnak ruangah a dik deuh in a si.
Lithium-ion battery nih cun a sangmi current dirhmun tangah lumnak a chuahter (a rangmi charge le a rangmi discharge telh chih in), cu nih cun a chunglei lumnak a kaiter. A lin tukmi hmun ah um cu battery riantuan ning a chiatter khawh, cu ah cun a thazaang le a thazaang a tlau kho. A tlangpi in, lithium tlau le a lum tukmi ah a cawlcangmi thilri hmuh ṭhannak nih thilti khawhnak tlaunak a chuahter, cun thazaang tlaunak cu chunglei ralchanhnak a karh caah a si. Lungthawhnak nih a uk khawh lo ahcun, lumnak a zam, cu nih cun thil sining cheukhat ahcun amah tein kanghnak asiloah puahnak tiang a chuahter khawh.
QSAR tuaktannak cu thilnung cawlcanghnak le thilri hna i an sining karlak pehtlaihnak hngalh khawhnak caah hmanmi tuaktannak asiloah tuaktannak model sernak lam a si. Design tuahmi molecule vialte cu an ttha bik in an ser hna i QSAR sining cheukhat cu PM6 level ah an tuak. Table 3 nih tuakmi QSAR fianternak cheukhat a langhter. Cu bantuk langhternak tahchunhnak hna cu charge, TDM, thazaang dihlak (E), ionization potential (IP), Log P, le polarizability (IP le Log P hngalh khawhnak formula caah Table 1 zoh).
Tuaktannak hmuhmi nih a langhter mi cu hlathlainak tuahmi thilri vialte hna cu an dirhmun ah an um caah an dihlak in an charge cu zero a si. A hmasa bik pehtlaihnak a si khomi caah, glycerol TDM cu 3PVA-(C10) 2Na Alg caah 2.788 Debye le 6.840 Debye a si, cu lio ah TDM man cu 17.990 Debye, 8.848 Debye, 5.874 Debye, 7.658 Debye le Debye bye ah 17.777 ah an karhter. 3PVA-(C10) 2Na Alg nih 1, 2, 3, 4 le 5 units glycerol he an i pehtlaih. TDM man a sang deuhdeuh ahcun pawngkam he aa pehtlaihnak a sang deuhdeuh.
A dihlak thazaang (E) zong tuak a si, cun glycerol le 3PVA-(C10)2 NaAlg E man cu -141.833 eV le -200092.503 eV an si ti an hmuh. Cu lio ah, 3PVA-(C10)2 NaAlg aiawhtu sining hna nih 1, 2, 3, 4 le 5 glycerol units he an i pehtlaih; E cu -996.837, -1108.440, -1238.740, -1372.075 le -1548.031 eV ah a cang. Glycerol dat karhternak nih thazaang dihlak a zorter i cucaah a lehrulhnak a karhter. Thazaang dihlak tuaktannak cungah hram bunh in, 3PVA-2Na Alg-5 Gly a simi model molecule cu a dang model molecule hna nakin a tthawng deuh tiah biachahnak an tuah. Hi thil cangmi hi an dirhmun he aa pehtlai. 3PVA-(C10)2NaAlg nih -COONa phu hnih lawng a ngeih, a dang sining hna nih -COONa phu pahnih an ngei nain OH phu zeimawzat an i put, cucu pawngkam he an i pehtlaihnak a karh tinak a si.
Cun, hi hlathlainak ah hin thilri vialte i ionization thazaang (IE) zong ruah chih an si. Ionization thazaang cu hlathlainak tuahmi model i a tthatnak tahnak caah a biapi mi tahfung pakhat a si. Electron pakhat kha molecule hmun pakhat in donghnak ngei lo tiang kalpi awkah a herhmi thazaang cu ionization thazaang tiah auh a si. Molecule i ionization (cucu reactivity) tlukruannak kha a aiawh. Ionization thazaang a sang deuhdeuh ahcun, a tlawm deuhdeuh. 3PVA-(C10)2NaAlg nih 1, 2, 3, 4 le 5 glycerol units he pehtlaihnak a tuahmi IE hmuhmi cu -9.256, -9.393, -9.393, -9.248 le -9.323 eV an si, cu lio ah glycerol le 3PVA(C10)2NaAlg(C10)Alg -55557557575656 eV an si. le -9.341 eV, ciocio. Glycerol chapnak nih IP man a zorter caah, molecule reactivity a karh, cu nih cun PVA/NaAlg/glycerol model molecule kha electrochemical thilri ah hman khawhnak a ṭhanchoter.
Table 3 chung i a panganak langhternak cu Log P a si, cucu tthencheunak coefficient logarithm a si i hlathlainak tuahmi sining cu ti a duhmi maw ti a duh lomi a si timi langhternak caah hmanmi a si. A ttha lomi Log P man nih ti a duhmi molecule a langhter, a sullam cu ti chungah fawi tein a rawk i organic solvents ah a rawk ttha lo tinak a si. A ttha mi man nih a kalhmi thil kalning a langhter.
Hmuhmi hmuhmi cungah hram bunh in, an Log P man (3PVA-(C10)2Na Alg − 1Gly, 3PVA-(C10)2Na Alg − 2Gly, 3PVA-(C10)2Na Alg − 3Gly, PVA-(C10)2Na Alg − 3Gly, PVA-(C10)(C10)(C10)-gly) caah, a sining vialte cu ti a duhmi an si tiah biachahnak tuah khawh a si 4Gly le 3PVA-(C10)2Na Alg − 5Gly) cu -3.537, -5.261, -6.342, -7.423 le -8.504 an si, cu lio ah glycerol i Log P man cu -1.081 lawng a si i 3PVA-(C10)2Na Alg -1003 lawng a si. A sullam cu hlathlainak tuahmi thilri sining hna cu a sining ah ti molecule pawl an i tel tikah aa thleng lai tinak a si.
A donghnak ah, thilri vialte i an i tthennak zong kha PM6 level ah semi-empirical phunglam hmangin tuak a si. Thilri tam deuh i an i tthen khawhnak cu thil phunphun cungah aa hngat ti kha a hlan ah theih a si cang. A biapi bikmi cu hlathlainak tuahmi thilri a ngan ning a si. 3PVA le 2NaAlg karlak i pehtlaihnak phunkhatnak aa telmi sining vialte caah (pehtlaihnak cu carbon atom nambar 10 hmangin a cang), glycerol chapnak in polarizability cu a tthancho. 1, 2, 3, 4 le 5 glycerol units he pehtlaihnak ruangah polarizability cu 29.690 Å in 35.076, 40.665, 45.177, 50.239 le 54.638 Å tiang a karh. Cucaah, a sang bikmi polarizability a ngeimi model molecule cu 3PVA-(C10)2NaAlg−5Gly a si ti hmuh a si, cun a niam bikmi polarizability a ngeimi model molecule cu 3PVA-(C10)2NaAlg a si, cucu 29.690 Å a si.
QSAR fianternak hna zohfelnak nih 3PVA-(C10)2NaAlg − 5Gly aiawhtu dirhmun cu a hmasa bik ruahnak cheuhnak pehtlaihnak caah a tthawng bikmi a si ti a langhter.
PVA trimer le NaAlg dimer karlak i a pahnihnak pehtlaihnak phun caah, a phichuak nih a langhter mi cu an charges cu a hlan i a hmasa bik pehtlaihnak caah ruahnak cheuhnak he aa lo. Inn saknak vialte nih electronic charge zero an ngei, cucu an dihlak in vawlei dirhmun ah an um tinak a si.
Table 4 ah langhter bantuk in, Term 1 Na Alg − 3PVA-Mid 1 Na Alg i TDM man (PM6 level ah tuakmi) cu 11.581 Debye in 15.756, 19.720, 21.756, 22.732, 15.757, 15.757, Term le Na Alg −1515 ah a karh. 3PVA-Mid 1 Na Alg cu 1, 2, 3, 4, 5, le 6 units glycerol he an i pehtlaih. Sihmanhsehlaw, thazaang dihlak cu glycerol unit zat a karh tikah a zor, cun Term 1 Na Alg − 3PVA- Mid 1 Na Alg nih glycerol unit zat (1 in 6) he pehtlaihnak a tuah tikah, thazaang dihlak cu − 996.985, − 1129.013, − 1267, − 1267, − 127. 1418.964, le − 1637.432 eV, ciocio.
A pahnihnak pehtlaihnak a si khomi caah, IP, Log P le polarizability zong PM6 theory level ah tuak an si. Cucaah, annih nih molecular reactivity a langhtertu a tthawng bikmi pathum an ruah. End 1 Na Alg-3PVA-Mid 1 Na Alg 1, 2, 3, 4, 5 le 6 glycerol units he aa pehtlaimi sining hna caah, IP cu −9.385 eV in −8.946, −8.848, −8.430, −9.537, −7.99 le −8.07V tiang a karh. Sihmanhsehlaw, tuakmi Log P man cu a niam deuh, zeicahtiah End 1 Na Alg-3PVA-Mid 1 Na Alg cu glycerol he an cawh caah a si. Glycerol dat 1 in 6 tiang a karh tikah, a man cu -3.643 si loin -5.334, -6.415, -7.496, -9.096, -9.861 le -10.53 ah a cang. A donghnak ah, polarizability data nih a langhter mi cu glycerol dat karhternak nih Term 1 Na Alg- 3PVA- Mid 1 Na Alg polarizability a karhter. Model molecule Term 1 Na Alg- 3PVA- Mid 1 Na Alg i a tthencheunak cu glycerol unit 6 he pehtlaihnak an tuah hnu ah 31.703 Å in 63.198 Å tiang a karh. A pahnihnak pehtlaihnak a si khomi ah glycerol unit karhternak cu atom tampi le a harmi sining um ko hmanh sehlaw, glycerol dat karhternak he riantuan ning a tthancho rih ko ti fehternak caah tuah a si ti hngalh a biapi. Cucaah, a ummi PVA/Na Alg/glycerin model nih lithium-ion battery pawl kha tlawmpal in a thlen khawh hna tiah chim khawh a si, asinain hlathlainak le tthanchonak tam deuh a herh rih.
Adsorbate he a cunglei i aa pehtlaimi thilti khawhnak sining langhternak le system karlak i aa dangmi pehtlaihnak hna kha tuaktannak nih atom pahnih karlak ah a ummi pehtlaihnak phun, intermolecular le intramolecular pehtlaihnak a harnak, le a cunglei le adsorbent i electron density phawtzamhnak kong hngalh a herh. QTAIM hlathlainak ah aa pehtlaimi atom hna karlak i pehtlaihnak a biapi tukmi hmun (BCP) ah electron tlawmtam cu a biapi tukmi a si. Electron charge density a sang deuhdeuh ahcun, covalent pehtlaihnak cu a fek deuhdeuh i, a tlangpi in, hi a biapi tukmi hmun hna ah electron density a sang deuhdeuh. Cun, electron thazaang dihlak (H(r)) le Laplace charge tlawmtam (∇2ρ(r)) pahnih hi 0 nak tlawm deuh an si ahcun, mah nih hin covalent (a tlangpi) pehtlaihnak a um ti a langhter. Khatlei kam in, ∇2ρ(r) le H(r) cu 0.54 nak tam an si tikah, a derthawmmi hydrogen pehtlaihnak, van der Waals thazaang le electrostatic pehtlaihnak tibantuk non-covalent (a kharmi vun) pehtlaihnak a um ti a langhter. QTAIM hlathlainak nih hmanthlak 7 le 8 ah langhtermi bantukin hlathlainak tuahmi sining hna ah covalent a si lomi pehtlaihnak hna an sining kha a langhter. Hlathlainak cungah hram bunh in, 3PVA − 2Na Alg le Term 1 Na Alg − 3PVA –Mid 1 Na Alg aiawhtu model molecule hna nih g unit dangdang he aa pehtlaimi molecule hna nakin a sang deuhmi dirhmun an langhter. Zeicatiah alginate sining ah a tam deuhmi non-covalent pehtlaihnak tampi hna cu electrostatic pehtlaihnak le hydrogen pehtlaihnak hna nih alginate kha a fonhmi thilri pawl kha a dirter khawh hna. Cun, kan hmuhmi nih 3PVA − 2Na Alg le Term 1 Na Alg − 3PVA –Mid 1 Na Alg model molecule le glycine karlak ah non-covalent pehtlaihnak a biapitnak a langhter, cu nih cun glycine nih hin composites vialte electronic pawngkam remhnak ah a biapi mi rian a ttuan ti a langhter.
Model molecule 3PVA − 2NaAlg nih (a) 0 Gly, (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, le (f) 5Gly he pehtlaihnak a tuahmi QTAIM hlathlainak.