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Lapud dakel so sodium resource, saray sodium-ion batteries (NIBs) et mangirerepresenta na maabig ya alternatibon solusyon parad panagtipon na enerhiya ed electrochemical. Diad kaplesan, say manunan babeng ed iyaaligwas na teknolohiya na NIB et say kakulangan na saray materyales ya electrode ya makapangipawil/makapangipaway na sodium ions ed andukey a panaon. Kanian, say getma na sayan impanaral et pian nausisa so epekto na panangiyarum na glycerol ed polyvinyl alcohol (PVA) tan sodium alginate (NaAlg) ya nanlaok bilang materyales na NIB electrode. Sayan impanaral et akasentro ed electronic, thermal, tan quantitative structure-activity relationship (QSAR) ya deskriptor na polymer electrolytes base ed PVA, sodium alginate, tan glycerol blends. Sarayan kablian et inimbestigaan ya uusaren so semi-empirical iran paraan tan density functional theory (DFT). Lapud say structural analysis et angipatnag na detalye na saray pidedeneng na PVA/alginate tan glycerol, say band gap energy (Eg) so inimbestigaan. Ipapanengneng na resulta ya say pangiyarum na glycerol et manresulta ed ibawas na Eg value ya anggad 0.2814 eV. Say molecular electrostatic potential surface (MESP) et mangipapanengneng na inkaapag-apag na saray rehyon ya mayaman tan makapuy so electron tan saray karga na molekula ed interon sistema na electrolyte. Saray thermal parameters ya inaral et kaiba so enthalpy (H), entropy (ΔS), heat capacity (Cp), Gibbs free energy (G) tan heat of formation. Niarum ni, pigaran quantitative structure-activity relationship (QSAR) descriptors a singa say total dipole moment (TDM), total energy (E), ionization potential (IP), Log P tan polarizability so inimbestigaan ed sayan impanaral. Impanengneng na resulta ya say H, ΔS, Cp, G tan TDM et dinmaak legan ya ondarakel so temperatura tan glycerol content. Kaleganan to, say petang na pormasyon, IP tan E et dinmaak, ya amaaligwas ed reactivity tan polarisability. Niarum ni, diad pangiyarum na glycerol, say boltahe na selula et inmatagey ed 2.488 V. Say kalkulasyon na DFT tan PM6 base ed epektibon gastos ya PVA/Na Alg glycerol-based electrolytes so mangipapanengneng ya sarag dan saliwen so lithium-ion ya baterya lapud multifunctionality da, balet kaukolan ni so kaaruman iran pananguman tan panagsukimat.
Anggaman saray lithium-ion batteries (LIBs) et malaknab ya uusaren, say aplikasyon da et walaan na dakel a limitasyon lapud antikey so bilay da, atagey so gastos da, tan saray kapagaan ed kaligenan. Saray sodium-ion batteries (SIBs) et nayarin magmaliw ya alternatibo ed LIBs lapud malaknab so pakawalaan da, abeban bili, tan ag-ira makasamal na sodium element. Saray sodium-ion batteries (SIBs) et nagmaliw ya lalon importantin sistema na panagtipon na enerhiya parad saray electrochemical devices1. Saray sodium-ion ya baterya et mandedependin maong ed saray electrolytes pian napagaan so transportasyon na ion tan makapawala na kuryente2,3. Saray likidon electrolytes et manunan tugyopen na metal salts tan organic solvents. Saray praktikal ya aplikasyon et mankaukolan na maalwar ya konsiderasyon ed kaligenan na saray likidon electrolyte, lalo la no say baterya et napapaarap ed thermal odino electrical stress4.
Saray sodium-ion batteries (SIBs) et iilaloan ya onsalat ed saray lithium-ion batteries diad magano lapud dakel so reserba ra ed dayat, ag-ira makasamal, tan abeba so gastos ed materyales. Say panagtipon na nanomaterials so amapeles ed inkiwala na data storage, electronic, tan optical devices. Dakel a literatura so angipatnag na aplikasyon na nanduruman nanostructures (alimbawa, metal oxides, graphene, nanotubes, tan fullerenes) ed saray sodium-ion ya baterya. Say panagsukimat et akasentro ed panagpaalagey na saray materyales ya anode, kaiba lay polymers, parad saray sodium-ion ya baterya lapud dakel so nagawaan da tan ag ira makaderal ed kaliberliber. Say interes ed panagsukimat ed lawak na saray rechargeable polymer batteries et seguradon ondarakel. Saray balon materyales ya polymer electrode ya walaan na nikadkaduman istruktura tan kablian et posiblin mangilukas na dalan parad saray teknolohiya ya ag makaderal ed kaliberliber ya panagtipon na enerhiya. Anggaman nanduruman materyales na polymer electrode so naeksplor ya usaren ed saray sodium-ion ya baterya, sayan lawak et wala ni ed gapoan na iyaaligwas to. Parad saray sodium-ion ya baterya, mas dakel nin materyales ya polymer ya walaan na nanduruman istruktura so kaukolan ya aralen. Base ed kaplesan ya pikakabat tayo ed mekanismo na panagsimpen na sodium ions ed saray materyales na polymer electrode, nayarin ipasen ya saray carbonyl groups, free radicals, tan heteroatoms ed conjugated system et nayarin manserbin aktibon pasen parad pidedeneng ed saray sodium ions. Kanian, importante so panggawa na balon polimer ya walaan na atagey a densidad na sarayan aktibon pasen. Say gel polymer electrolyte (GPE) et sakey ya alternatibon teknolohiya ya mamaaligwas ed inka-reliable na baterya, ion conductivity, anggapoy leakage, atagey ya flexibility, tan maong ya performance12.
Saray polymer matrices et walaan na saray materyales a singa say PVA tan polyethylene oxide (PEO)13. Say gel permeable polymer (GPE) et mamatunda ed likidon electrolyte ed polymer matrix, ya mamapaabeba ed peligro na itagas no ikompara ed saray komersyal ya separator14. Say PVA et sakey a sintetikon polimer ya nabulok. Atagey so permittivity to, agmabli tan aliwan makasamal. Say materyal et kabkabat lapud saray kablian ton manporma na pelikula, inkapekder na kemikal tan inkapeket to. Wala met so functional (OH) groups to tan atagey ya cross-linking potential density15,16,17. Say polymer blending, plasticizer addition, composite addition tan in situ polymerization techniques so inusar pian napaaligwas so konduktibidad na PVA-based polymer electrolytes pian nabawasan so matrix crystallinity tan napalaknab so chain flexibility18,19,20.
Say panagtimpla et sakey ya importantin paraan pian nawalaan na polymeric iran materyales parad saray aplikasyon ed industriya. Saray polymer blend et mabetbet ya uusaren pian: (1) napaaligwas so panagproseso na saray natural ya polymer diad saray aplikasyon ed industriya; (2) paaligwasen so kemikal, pisikal, tan mekanikal iran kablian na saray materyales ya nabulok; tan (3) mibagay ed maples ya panguuman na pankaukolan parad balon materyales ed industriya na panagbalot na naakan. Aliwan singa say copolymerization, say polymer blending et sakey a proseso ya abeban gastos ya manguusar na simplin pisikal iran proseso imbes ya komplikadon kemikal iran proseso pian nadampot iray labay ya kablian21. Pian makagawa na homopolymers, saray nanduruman polymers et nayarin mitongtong panamegley na dipole-dipole forces, hydrogen bonds, odino charge-transfer complexes22,23. Saray timpla ya gawad natural tan sintetikon polimer et makapangitipon na maong ya biocompatibility tan ekselentin mekanikal iran kablian, ya mamawala na superyor a materyales ed abeban gastos ed produksyon24,25. Kanian, baleg so interes ed panggawa na biorelevant polymeric materials diad panamegley na panlalaok na sintetiko tan natural iran polymer. Say PVA et nayarin ipila ed sodium alginate (NaAlg), cellulose, chitosan tan starch26.
Say sodium alginate et natural ya polimer tan anionic polysaccharide ya inala ed marine brown algae. Say sodium alginate et tugyopen na β-(1-4)-linked D-mannuronic acid (M) tan α-(1-4)-linked L-guluronic acid (G) ya inorganisa ed homopolymeric forms (poly-M tan poly-G) tan heteropolymeric blocks (MG o GM)27. Say karga tan relatibon ratio na M tan G blocks et walay baleg ya epekto to ed kemikal tan pisikal iran kablian na alginate28,29. Say sodium alginate et malaknab ya uusaren tan aaralen lapud biodegradability, biocompatibility, abeban gastos, maong ya film-forming properties, tan aliwan makasamal. Balet, say baleg a bilang na free hydroxyl (OH) tan carboxylate (COO) ya grupo ed alginate chain so manggagawa ed alginate ya hydrophilic. Balet, say alginate et walaan na makapuy iran mekanikal a kablian lapud inka-brittle tan inka-rigid to. Kanian, say alginate et nayarin ipila ed arum ya sintetikon materyales pian napaaligwas so inkasensitibo ed danum tan saray mekanikal a kablian to30,31.
Antis ya mandesinyo na balon materyales ya electrode, saray kalkulasyon na DFT et mabetbet ya uusaren pian naseguro so posibilidad na panaggawa na balon materyales. Niarum ni, manguusar na molecular modeling iray sientista pian nakumpirma tan nahulaan iray resulta na eksperimento, makatipid na panaon, nabawasan so basura na kemikal, tan nahulaan so ugali na pidedeneng32. Say molecular modeling et nagmaliw ya mabiskeg tan importantin sanga na siensia ed dakel a lawak, kaiba lay siensia na materyales, nanomaterials, computational chemistry, tan panagdiskobre na tambal33,34. Diad pangusar na saray programa ed panagmodelo, saray sientista et direktan makagamor na datos na molekula, kaiba lay enerhiya (petang na inkaporma, potensyal na ionization, enerhiya na panag-aktibo, tan arum ni) tan geometry (anggulo na bond, karukey na bond, tan anggulo na torsion)35. Niarum ni, saray electronic properties (charge, HOMO tan LUMO band gap energy, electron affinity), spectral properties (characteristic vibrational modes tan intensities a singa say FTIR spectra), tan bulk properties (volume, diffusion, viscosity, modulus, tan arum ni)36 et nayarin kalkulaen.
Say LiNiPO4 et mangipapanengneng na posiblin bentaha to ed kompetisyon tod lithium-ion battery positive electrode materials lapud atagey ya energy density to (working voltage ya manga 5.1 V). Pian sigpot ya nausar so bentaha na LiNiPO4 ed rehyon na atagey a boltahe, kaukolan ya iyabeba so boltahe ya mankikimey lapud say kaplesan ya gagawaen ya atagey a boltahe ya electrolyte et makapansiansia labat ya medyo malet ed saray boltahe ya abeba nen 4.8 V. Zhang et al. inimbestigaan so doping na amin ya 3d, 4d, tan 5d transition metals ed Ni site na LiNiPO4, pinili iray doping pattern ya walaan na ekselentin electrochemical performance, tan in-adjust so working voltage na LiNiPO4 legan ya mansiasiansia so relatibon stability na electrochemical performance to. Say sankaabebaan ya working voltages ya naala ra et 4.21, 3.76, tan 3.5037 parad Ti, Nb, tan Ta-doped LiNiPO4, unong ed inkauksoy da.
Kanian, say getma na sayan impanaral et pian nausisa so epekto na glycerol bilang plasticizer ed saray electronic properties, QSAR descriptors tan thermal properties na PVA/NaAlg system ya uusaren so quantum mechanical calculations parad aplikasyon to ed saray rechargeable ion-ion batteries. Say molekular ya pidedeneng na PVA/NaAlg model tan glycerol et inaral ya inusar so quantum atomic theory of molecules (QTAIM) nen Bader.
Say modelo na molekula ya mangirerepresenta ed pidedeneng na PVA ed NaAlg insan ed glycerol et in-optimize ya inusar so DFT. Say modelo et kinalkula ya inusar so Gaussian 0938 software diad Spectroscopy Department, National Research Center, Cairo, Egypt. Saray modelo et in-optimize ya inusar so DFT diad B3LYP/6-311G(d, p) level39,40,41,42. Pian naseguro so pidedeneng na saray modelon inaral, saray frequency study ya ginawa ed parehon lebel na teorya so mangipapanengneng na inkapekder na optimized geometry. Say kiwawala na negatibon frequency ed amin ya inebalwar iran frequency so mangipapabitar ed naisip ya istruktura ed tua ya positibon minima ed tapew na potensyal ya enerhiya. Saray pisikal ya parametro a singa say TDM, HOMO/LUMO band gap energy tan MESP et kinalkula ed parehon quantum mechanical level na teorya. Niarum ni, pigaran thermal parameters a singa say pinal ya petang na inkaporma, libren enerhiya, entropy, enthalpy tan kapasidad na petang so kinalkula ya inusar iray pormula ya niiter ed Table 1. Saray inaral ya modelo et insulong ed quantum theory of atoms in molecules (QTAIM) analysis pian naamtaan iray interaksion ya nagagawa ed tapew na saray inaral ya istruktura. Sarayan kalkulasyon et ginawa ya inusar so “output=wfn” ya ganggan ed Gaussian 09 software code insan in-visualize ya inusar so Avogadro software code43.
No say E et say enerhiya ed loob, say P et say presyon, say V et say karakel, say Q et say pansasalat na petang ed baetan na sistema tan say kaliberliber to, say T et say temperatura, say ΔH et say pananguman na enthalpy, say ΔG et say pananguman na libren enerhiya, say ΔS et say pananguman na entropy, say a tan b et saray vibrational parameters, say q et say atomic charge, tan say C et say dentomic electronity, 4545. Diad kaunoran, saray parehon istruktura so in-optimize tan saray QSAR parameters so kinalkula ed PM6 level ya inusar so SCIGRESS software code46 diad Spectroscopy Department na National Research Center ed Cairo, Egypt.
Diad akaunan kimey mi47, inebalwar mi so sanka-probablian a modelo ya mangidedeskribe ed pidedeneng na taloran yunit na PVA ed duaran yunit na NaAlg, ya say glycerol so onkikiwas bilang plasticizer. Unong ya asalambit ed tagey, walay duaran posibilidad na pidedeneng na PVA tan NaAlg. Say duaran modelo, ya tatawagen ya 3PVA-2Na Alg (base ed carbon number 10) tan Term 1Na Alg-3PVA-Mid 1Na Alg, so walaan na sankamelagan ya energy gap value48 no ikompara ed arum ya istruktura ya inkonsidera. Kanian, say epekto na Gly addition ed sanka-posiblin modelo na PVA/Na Alg blend polymer et inimbestigaan ya inusar so unor ya duaran istruktura: 3PVA-(C10)2Na Alg (tatawagen ya 3PVA-2Na Alg parad kasimplian) tan Term 1 Na Alg − 3PVA-Mid 1 Na Alg. Unong ed literatura, say PVA, NaAlg tan glycerol et makapanggawa labat na makapuy iran hydrogen bonds ed baetan na saray hydroxyl functional groups. Lapud say PVA trimer tan say NaAlg tan glycerol dimer et walaan na pigaran OH groups, say contact et nayarin nagawa panamegley na sakey ed saray OH groups. Ipapanengneng na Figure 1 so pidedeneng na modelon glycerol molecule tan say model molecule ya 3PVA-2Na Alg, tan say Figure 2 et mangipapanengneng na ginawan modelo na pidedeneng na model molecule ya Term 1Na Alg-3PVA-Mid 1Na Alg tan nanduruman konsentrasyon na glycerol.
Saray sankaabigan ya istruktura: (a) Gly tan 3PVA − 2Na Alg et mibabali ed (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, tan (f) 5 Gly.
Saray pinaaligwas ya istruktura na Term 1Na Alg- 3PVA –Mid 1Na Alg ya mibabali ed (a) 1 Gly, (b) 2 Gly, (c) 3 Gly, (d) 4 Gly, (e) 5 Gly, tan (f) 6 Gly.
Say enerhiya na electron band gap et sakey ya importantin parameter ya ikonsidera no aaralen so reactivity na antokaman ya materyales na electrode. Lapud dedeskribien na saya so ugali na saray electron no say materyal et napapaarap ed saray pananguman ed paway. Kanian, kaukolan ya kalkulaen so electron band gap energies na HOMO/LUMO parad amin ya istruktura ya inaral. Ipapanengneng na Table 2 so pananguman ed HOMO/LUMO ya enerhiya na 3PVA-(C10)2Na Alg tan Term 1Na Alg − 3PVA- Mid 1Na Alg lapud inyarum na glycerol. Unong ed ref47, say Eg value na 3PVA-(C10)2Na Alg et 0.2908 eV, bangta say Eg value na istruktura ya mangipapatnag na posibilidad na komaduan interaksion (salanti, Term 1Na Alg − 3PVA- Mid 1Na Alg) et 0.5706 eV.
Balet, aromog ya say inyarum na glycerol et nanresulta ed daiset ya pananguman ed Eg value na 3PVA-(C10)2Na Alg. Nen say 3PVA-(C10)2NaAlg et akitongtong ed 1, 2, 3, 4 tan 5 glycerol units, say Eg values ​​to et nagmaliw ya 0.302, 0.299, 0.308, 0.289 tan 0.281 eV, unong ed inkauksoy da. Balet, walay makanakanan pakatalos ya kayari na inyarum na 3 glycerol units, say balor na Eg et nagmaliw ya mas melag nen say 3PVA-(C10)2Na Alg. Say modelo ya mangirerepresenta ed pidedeneng na 3PVA-(C10)2Na Alg ed limaran yunit na glycerol so sanka-posiblin modelo na pidedeneng. Kabaliksan na saya ya legan ya ondarakel so glycerol units, ondarakel met so posibilidad na pidedeneng.
Balet, parad komaduan posibilidad na pidedeneng, say HOMO/LUMO ya enerhiya na saray modelon molekula ya mangirerepresenta ed Term 1Na Alg − 3PVA –Mid 1Na Alg- 1Gly, Term 1Na Alg − 3PVA –Mid 1Na Alg- 2Gly, Term 1Na Alg − 3PVA – 1Na Alg- Na Algly, Term 1Na Say Alg − 3PVA –Mid 1Na Alg- 4Gly, Term 1Na Alg − 3PVA –Mid 1Na Alg- 5Gly tan say Term 1Na Alg − 3PVA –Mid 1Na Alg- 6Gly et magmaliw ya 1.343, 1.34 7, 0.976, 0.607, 0.044, tan 46. balang sakey. Ipapanengneng na Table 2 so kinalkula ya HOMO/LUMO band gap energies parad amin ya istruktura. Sakey ni, say parehon ugali na saray posibilidad na pidedeneng na inmunan grupo so naulit dia.
Say band theory ed solid state physics et ibabaga ton no onbabawas so band gap na electrode material, ondarakel so electronic conductivity na materyal. Say doping et sakey a kaslakan a paraan pian nabawasan so band gap na sodium-ion cathode materials. Jiang et al. inusar so Cu doping pian napaaligwas so electronic conductivity na β-NaMnO2 layered materials. Diad impangusar na kalkulasyon na DFT, aromog dan say doping et amawala na band gap na materyal manlapud 0.7 eV ya anggad 0.3 eV. Ipapanengneng na saya ya say Cu doping et mamaaligwas ed electronic conductivity na β-NaMnO2 material.
Say MESP et kabaliksan na enerhiya na pankakasakey ed baetan na panagbunog na molekular a karga tan sakey a positibon karga. Say MESP et ipapasen ya epektibon kagawaan parad pakatalos tan pangiter na kabaliksan ed saray kemikal a kablian tan inka-reaktibo. Say MESP et nayarin usaren pian natalosan so mekanismo na pidedeneng na saray materyales ya polymeric. Say MESP et mangidedeskribe ed inkaapag-apag na karga ed loob na compound ya aaralen. Niarum ni, say MESP et mangiiter na impormasyon nipaakar ed saray aktibon pasen ed saray materyales ya aaralen32. Ipapanengneng na Figure 3 so MESP plots na 3PVA-(C10) 2Na Alg, 3PVA-(C10) 2Na Alg − 1Gly, 3PVA-(C10) 2Na Alg − 2Gly, 3PVA-(C10) 2Na Alg − 3Gly, 3PVA-(C10) 2Na Alg − 2Gly, tan Algly 3PVA-(C10) 2Na Alg − 5Gly ya inpredikta ed B3LYP/6-311G(d, p) ya lebel na teorya.
MESP contours ya kinalkula ed B3LYP/6-311 g(d, p) parad (a) Gly tan 3PVA − 2Na Alg ya mibabali ed (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, tan (f) 5 Gly.
Kaleganan to, ipapanengneng na Fig. 4 so kalkuladon resulta na MESP parad 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 – Mid 1Na Alg- 1Gly Term 1Na Alg-3PVA – Mid 1Na Alg − 4Gly, Term 1Na Alg- 3PVA – Mid 1Na Alg- 5gly tan Term 1Na Alg-3PVA – Mid 1Na Alg − 6Gly, unong ed inkauksoy da. Say kinalkula ya MESP et nirepresenta bilang sakey a contour behavior. Saray linya na kurti et nirepresenta na nanduruman kolor. Kada kolor et mangirerepresenta na nanduruman balor na electronegativity. Say ambalangan kolor et mangipapanengneng na saray pasen ya electronegative o reactive. Balet, say kolor ya duyaw et mangirerepresenta ed neutral iran pasen 49, 50, 51 ed istruktura. Say resulta na MESP so angipatnag ya say reaktibo na 3PVA-(C10)2Na Alg et dinmaak legan ya ondarakel so kolor ya ambalanga ed kaliberliber na saray inaral ya modelo. Balet, say kolor ya ambalanga ed MESP map na Term 1Na Alg-3PVA – Mid 1Na Alg model molecule et onbabawas lapud pidedeneng na nanduruman glycerol content. Say panguman na kolor ya ambalanga ed kaliberliber na iproproponin istruktura et mangipapatnag na reaktibo, bangbalet say idarakel na inka-intensibo so mangikukumpirma ed idakel na electronegativity na 3PVA-(C10)2Na Alg model molecule lapud idakel na glycerol content.
B3LYP/6-311 g(d, p) kinalkula so MESP Term na 1Na Alg-3PVA-Mid 1Na Alg ya mibabali ed (a) 1 Gly, (b) 2 Gly, (c) 3 Gly, (d) 4 Gly, (e) 5 Gly, tan (f) 6 Gly.
Amin ya iproproponin istruktura et walaan na saray thermal parameters da a singa say enthalpy, entropy, heat capacity, free energy tan heat of formation ya kinalkula ed nanduruman temperatura manlapud 200 K anggad 500 K. Pian nideskribe so ugali na saray pisikal a sistema, nilikud ed panaral ed electronic behavior da, kaukolan met ya aralen so thermal behavior da bilang sakey a function na temperatura ed balang sakey, ya nayarin pansengegan na pidedeneng da ed balang sakey kinalkula base ed saray equation ya walad Table 1. Say panaral ed sarayan thermal parameters et ipapasen ya importantin pakapatnagan na inka-responsive tan inka-establi na saratan a pisikal a sistema ed nanduruman temperatura.
Nipaakar ed enthalpy na PVA trimer, unona et onreak ed NaAlg dimer, insan diad OH group ya akapeket ed carbon atom #10, tan diad kaunoran et diad glycerol. Say enthalpy et sakey a sukat na enerhiya ed sakey a sisteman thermodynamic. Say enthalpy et mipara ed dagup na petang ed sakey a sistema, ya mipara ed loob na enerhiya na sistema tan say produkto na karakel tan presyon to. Diad arum a salita, say enthalpy et mangipapanengneng no panon karakel so petang tan kimey ya iyarum o naekal ed sakey a substansia52.
Ipapanengneng na Figure 5 so panguuman na enthalpy legan na reaksion na 3PVA-(C10)2Na Alg ya walaan na nanduruman konsentrasyon na glycerol. Saray abbreviation ya A0, A1, A2, A3, A4, tan A5 et mangirerepresenta ed saray modelon molekula ya 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, tan 3PVA-(C10)2Na Alg − 5Gly, unong ed inkauksoy da. Ipapanengneng na Figure 5a ya say enthalpy et ondarakel no ondarakel so temperatura tan say glycerol content. Say enthalpy na istruktura ya mangirerepresenta ed 3PVA-(C10)2NaAlg − 5Gly (salanti, A5) ed 200 K et 27.966 cal/mol, bangta say enthalpy na istruktura ya mangirerepresenta ed 3PVA- 2NaAlg ed 200 K et 13.490 cal/mol. Kaunoran, lapud positibo so enthalpy, sayan reaksion et endothermic.
Say entropy et kabaliksan na sukat na ag nagamoran ya enerhiya ed sakey ya akasara ya sistema na thermodynamic tan mabetbet ya ipapasen ya sukat na inkagulo na sistema. Ipapanengneng na Figure 5b so panguman na entropy na 3PVA-(C10)2NaAlg ed temperatura tan no panon itan ya mibabali ed nanduruman glycerol units. Ipapanengneng na graph ya say entropy et manguuman ya linear legan ya ondarakel so temperatura manlapud 200 K ya anggad 500 K. Malinew ya ipapanengneng na Figure 5b ya say entropy na 3PVA-(C10)2Na Alg model et onkukurang ed 200 cal/K/mol ed 200 K lapud say 3PVA-(C10)2Na Alg model et mangipapatnag na daiset ya disorder. No ondarakel so temperatura, say 3PVA-(C10)2Na Alg model et magmaliw ya magulo tan mangipapaliwawa ed itatagey na entropy no ondarakel so temperatura. Sakey ni, mapatnag ya say istruktura na 3PVA-C10 2Na Alg- 5 Gly so walaan na sankatageyan ya entropy value.
Say parehon kalareker so naobserbaan ed Figure 5c, ya mangipapanengneng na panguman na kapasidad na petang ed temperatura. Say heat capacity et say karakel na petang ya nakaukolan pian nauman so temperatura na sakey a substansia na 1 °C47. Ipapanengneng na Figure 5c so pananguman ed kapasidad na petang na modelon molekula ya 3PVA-(C10)2NaAlg lapud saray pidedeneng ed 1, 2, 3, 4, tan 5 ya glycerol units. Ipapanengneng na pigura ya say kapasidad na petang na modelon 3PVA-(C10)2NaAlg et ondarakel ya linear ed temperatura. Say naobserbaan ya idakel na heat capacity legan ya ondarakel so temperatura et lapud phonon thermal vibrations. Niarum ni, walay ebidensya ya say idakel na glycerol content et mangitonton ed idakel na heat capacity na model 3PVA-(C10)2NaAlg. Sakey ni, ipapanengneng na istruktura ya say 3PVA-(C10)2NaAlg−5Gly so walaan na sankatageyan ya kapasidad na petang no ikompara ed arum ya istruktura.
Saray arum ya parametro a singa say libren enerhiya tan pinal a petang na inkaporma so kinalkula parad saray inaral ya istruktura tan nipanengneng ed Figure 5d tan e, unong ed inkauksoy da. Say unor ya petang na inkaporma et say petang ya nibulos o nasesepsep legan na inkaporma na puron substansia manlapud saray kabiangan to diad silong na pirmin presyon. Say libren enerhiya et nayarin ipaliwawa bilang sakey a kablian a mipara ed enerhiya, salanti, say balor to et mandedepende ed karakel na substansia ed kada thermodynamic state. Say libren enerhiya tan petang na inkaporma na 3PVA-(C10)2NaAlg−5Gly so sankaabebaan tan -1318.338 tan -1628.154 kcal/mol, unong ed inkauksoy da. Diad pidumaan, say istruktura ya mangirerepresenta ed 3PVA-(C10)2NaAlg so walaan na sankatageyan ya free energy tan heat of formation values ​​ya -690.340 tan -830.673 kcal/mol, no ikompara ed arum ya istruktura. Unong ed nanengneng ed Figure 5, nanduruman thermal properties so manguuman lapud pidedeneng to ed glycerol. Say Gibbs free energy et negatibo, ya mangipapanengneng ya say iproproponin istruktura et malet.
Say PM6 et kinalkula to ray thermal parameters na puron 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) Gly A3-33 (C10) 2Na Alg − 4 Gly (model A4), tan 3PVA- (C10) 2Na Alg − 5 Gly (model A5), no iner (a) et say enthalpy, (b) entropy, (c) kapasidad na petang, (d) libren enerhiya, tan (e) petang na inkaporma.
Diad biek a dapag, say komaduan paraan na pidedeneng na PVA trimer tan dimeric NaAlg et nagagawa ed terminal tan middle OH groups ed istruktura na PVA trimer. Singa ed inmunan grupo, saray thermal parameters et kinalkula ya inusar so parehon lebel na teorya. Ipapanengneng na Figure 6a-e so pandurumaan na enthalpy, entropy, kapasidad na petang, libren enerhiya tan, diad kaunoran, petang na inkaporma. Ipapanengneng na saray pigura 6a-c ya say enthalpy, entropy tan heat capacity na Term 1 NaAlg-3PVA-Mid 1 NaAlg et walaan na parehon ugali ed inmunan grupo no mibabali ed 1, 2, 3, 4, 5 tan 6 glycerol units. Sakey ni, kalkalnan ondarakel so balor da legan ya ondarakel so petang. Niarum ni, diad iproproponin Term 1 Na Alg − 3PVA-Mid 1 Na Alg model, say enthalpy, entropy tan heat capacity values ​​et dinmaak legan ya ondarakel so glycerol content. Saray abbreviation ya B0, B1, B2, B3, B4, B5 tan B6 et mangirerepresenta ed saray onggendan ya istruktura: 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 1 Na Alg − 1 Gly Alg- 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 tan Term 1 Na Alg- 3PVA- Mid 1 Na Alg − 6 Gly. Unong ed nanengneng ed Fig. 6a-c, mapatnag ya ondarakel so balor na enthalpy, entropy tan kapasidad na petang legan ya ondarakel so bilang na glycerol units manlapud 1 anggad 6.
Kinalkula na PM6 so thermal parameters na puron 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 (model B2), Term PVA-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), tan Term 1 Na Alg- 3PVA- Mid 1 Na Alg – 6 Gly (model B5), kaiba lay enpy (b) entropy, (c) kapasidad na petang, (d) libren enerhiya, tan (e) petang na inkaporma.
Niarum ni, say istruktura ya mangirerepresenta ed Term 1 Na Alg- 3PVA- Mid 1 Na Alg- 6 Gly so walaan na sankatageyan a balor na enthalpy, entropy tan heat capacity no ikompara ed arum ya istruktura. Diad saratan, say balor da et inmatagey manlapud 16.703 cal/mol, 257.990 cal/mol/K tan 131.323 kcal/mol ed Term 1 Na Alg − 3PVA- Mid 1 Na Alg ya anggad 33.223 cal/mol, 420.038 cal/mol/mol/mol/mol diad Term 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly, unong ed inkauksoy da.
Balet, ipapanengneng na Figures 6d tan e so pandepende na temperatura na libren enerhiya tan say pinal ya petang na inkaporma (HF). Say HF et nayarin ipaliwawa bilang say panguuman na enthalpy ya nagagawa no say sakey a mole na sakey a substansia et naporma manlapud saray elemento to diad silong na natural tan estandarten kondisyon. Napatnagan ed pigura ya say libren enerhiya tan say pinal ya petang na inkaporma na amin ya inaral ya istruktura et mangipapanengneng na linear ya dependensia ed temperatura, salanti, kalkalna tan linear iran ondarakel no ondarakel so temperatura. Niarum ni, akumpirma met na pigura ya say istruktura ya mangirerepresenta ed Term 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly so walaan na sankaabebaan ya libren enerhiya tan sankaabebaan ya HF. Parehon inmabeba so duaran parametro manlapud -758.337 ya anggad -899.741 K cal/mol ed terminon 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly ya anggad -1,476.591 tan -1,828.523 K cal/mol. Mapatnag ed saray resulta ya say HF et onbabawas no ondarakel so glycerol units. Kabaliksan na saya a lapud idarakel na saray grupon mankikimey, ondarakel met so reactivity kanian mas daiset so enerhiyan nakaukolan pian nagawaan so reaksion. Saya so mamepekder ya say plasticized PVA/NaAlg et nayarin usaren ed saray baterya lapud atagey so reactivity to.
Diad inkalapagan, say epekto na temperatura et naapag ed duaran klase: saray epekto na abeban temperatura tan saray epekto na atagey a temperatura. Say epekto na abeban temperatura et nalilikna ed saray bansan walad atagey a latitud, a singa say Greenland, Canada, tan Russia. No panaoy ambetel, say temperatura na dagem ed paway na sarayan pasen et abeba nen say zero degrees Celsius. Say karukey na bilay tan performance na lithium-ion ya baterya et nayarin naapektoan na abeban temperatura, lalo la ed saramay uusaren ed saray plug-in hybrid electric vehicles, pure electric vehicles, tan hybrid electric vehicles. Say biahe ed liwang et sananey nin ambetel ya kaliberliber ya mankaukolan na lithium-ion ya baterya. Singa bilang, say temperatura ed Mars et nayarin onleksab ed -120 degrees Celsius, ya sakey a baleg ya babeng ed pangusar na lithium-ion ya baterya ed saray spacecraft. Say abeban temperatura na operasyon et nayarin pansengegan na ibawas na charge transfer rate tan chemical reaction activity na lithium-ion batteries, ya manresulta ed ibawas na diffusion rate na lithium ions ed loob na electrode tan ionic conductivity ed electrolyte. Sayan inkagba so manresulta ed ibawas na kapasidad tan pakayari na enerhiya, tan no maminsan et nabawasan ni ingen so performance53.
Say epekto na atagey a temperatura et nagagawa ed mas malaknab a klase na aplikasyon, kaiba lay atagey tan abeban temperatura, bangta say abeban temperatura ya epekto et manunan limitado ed abeban temperatura na aplikasyon. Say epekto na abeban temperatura et manunan nadetermina ed temperatura na kaliberliber, bangbalet say epekto na atagey a temperatura et mas suston nadetermina ed atagey a temperatura ed loob na lithium-ion ya baterya legan ya mankikimey.
Saray lithium-ion ya baterya et mamapawala na petang no atagey so kuryente (kaiba lay maples ya panagkarga tan maples ya panagdischarge), ya sengegan na itatagey na temperatura ed loob. Say pakawalaan na atagey a temperatura et nayarin pansengegan met na pakaandi na performance na baterya, kaiba lay pakaandi na kapasidad tan pakayari. Kaslakan, say pakaandi na lithium tan say pakabawi na saray aktibon materyales ed atagey a temperatura et manresulta ed pakaandi na kapasidad, tan say pakaandi na pakayari et lapud idakel na resistensya ed loob. No ag nakontrol so temperatura, nagawa so thermal runaway, ya diad arum a kaso et nayarin manresulta ed biglan pakapoolan odino pakasabog ni ingen.
Say kalkulasyon na QSAR et sakey a paraan na panagmodelo ed panagkuenta odino matematika ya uusaren pian naamtaan so siglaotan na aktibidad na bilay tan saray kablian na istruktura na saray compound. Amin ya adesinyo iran molekula et in-optimize tan pigaran QSAR properties et kinalkula ed PM6 level. Say Table 3 et mangilista na pigara ed saray kinalkula ya QSAR descriptors. Saray alimbawa na saratan a deskriptor et say charge, TDM, total energy (E), ionization potential (IP), Log P, tan polarizability (nengnengen so Table 1 parad saray pormula pian naamtaan so IP tan Log P).
Ipapanengneng na resulta na kalkulasyon ya say dagup na karga na amin ya inaral ya istruktura et zero lapud wala ra ed ground state. Parad inmunan probabilidad na pidedeneng, say TDM na glycerol et 2.788 Debye tan 6.840 Debye parad 3PVA-(C10) 2Na Alg, bangbalet say balor na TDM et inmatagey ed 17.990 Debye, 8.848 Debye, 5.874 Debye, 7.658 Debye tan Debye nen Debye nen 2.77.77. Say 3PVA-(C10) 2Na Alg et akitongtong ed 1, 2, 3, 4 tan 5 ya yunit na gliserol, unong ed inkauksoy da. No mas atagey so TDM value, mas atagey so reactivity to ed kaliberliber.
Say kabuoan ya enerhiya (E) et kinalkula met, tan say E values ​​na glycerol tan 3PVA-(C10)2 NaAlg et aromog ya -141.833 eV tan -200092.503 eV, unong ed inkauksoy da. Balet, saray istruktura ya mangirerepresenta ed 3PVA-(C10)2 NaAlg et mibabali ed 1, 2, 3, 4 tan 5 glycerol units; Say E et magmaliw ya -996.837, -1108.440, -1238.740, -1372.075 tan -1548.031 eV, unong ed inkauksoy da. Say pamarakep ed glycerol content et manresulta ed ibawas na enerhiya tan diad ontan et ondarakel so reactivity. Base ed kalkulasyon na kabuoan ya enerhiya, naisip ya say modelon molekula, ya 3PVA-2Na Alg-5 Gly, et mas reaktibo nen saray arum ya modelon molekula. Sayan nagagawa et misiglaotan ed istruktura ra. Say 3PVA-(C10)2NaAlg et walaan labat na duaran -COONa a grupo, bangta saray arum ya istruktura et walaan na duaran -COONa a grupo balet ta walaan na pigaran OH a grupo, a mankabaliksan ya ondarakel so reaktibo ra ed kaliberliber.
Niarum ni, saray enerhiya na ionization (IE) na amin ya istruktura so ikonsidera ed sayan impanaral. Say enerhiya na ionization et sakey ya importantin parameter pian nasukat so reactivity na inaral ya modelo. Say enerhiyan nakaukolan pian makagalaw so sakey ya electron manlapud sakey a punto na molekula ya anggad andi-anggaan et tatawagen ya ionization energy. Irerepresenta na saya so laknab na ionization (salanti, reactivity) na molekula. No mas atagey so enerhiya na ionization, mas abeba so reactivity. Say resulta na IE na 3PVA-(C10)2NaAlg ya mibabali ed 1, 2, 3, 4 tan 5 glycerol units et -9.256, -9.393, -9.393, -9.248 tan -9.323 eV, bangta saray IE na glycerol tan 3.323 eV(C10)2NaAlg et -5.393 eV tan -9.341 eV, unong ed inkauksoy da. Lapud say inyarum na glycerol et nanresulta ed ibabawas na IP value, say molecular reactivity et dinmaak, ya mamaaligwas ed pakausar na PVA/NaAlg/glycerol model molecule ed saray electrochemical devices.
Say komaliman deskriptor ed Table 3 et say Log P, ya saya so logarithm na partition coefficient tan uusaren pian ideskribe no kasin say istruktura ya aaralen et hydrophilic odino hydrophobic. Say negatibon Log P value et mangipapanengneng na hydrophilic molecule, kabaliksan to ya mainomay ya natunaw ed danum tan ag tanton natunaw ed organic solvents. Say positibon balor et mangipapanengneng na kabaliktaran a proseso.
Base ed saray naala ya resulta, nayarin konklusyonan ya amin ya istruktura et hydrophilic, lapud saray Log P values ​​da (3PVA-(C10)2Na Alg − 1Gly, 3PVA-(C10)2Na Alg − 2Gly, 3PVA-(C10)2Na Alg − 3Gly, 3PVA-(C10)2Na Alg − 3Gly, PVA-(C10)(C10)(C10) Say 4Gly tan 3PVA-(C10)2Na Alg − 5Gly) et -3.537, -5.261, -6.342, -7.423 tan -8.504, unong ed inkauksoy da, bangta say Log P value na glycerol et -1.081 labat tan say 3PVA-(C10)2Na Alg −1030 labat. Kabaliksan na saya ya manguman so kablian na istruktura ya aaralen legan ya onloob iray molekula na danum ed istruktura to.
Diad kaunoran, say polarizabilities na amin ya istruktura et nakalkula met ed PM6 level ya uusaren so semi-empirical a paraan. Naimano la nensaman ya say polarizability na maslak a materyales et mandedepende ed nanduruman bengatla. Say sankaimportantian et say karakel na istruktura ya aaralen. Parad amin ya istruktura ya mangilalanor ed unonan klase na pidedeneng na 3PVA tan 2NaAlg (say pidedeneng et nagagawa panamegley na carbon atom number 10), say polarisability et napaaligwas diad pangiyarum na glycerol. Say polarizability et ondarakel manlapud 29.690 Å ya anggad 35.076, 40.665, 45.177, 50.239 tan 54.638 Å lapud saray pidedeneng ed 1, 2, 3, 4 tan 5 glycerol units. Kanian, aromog ya say modelon molekula ya walaan na sankatageyan a polarisability et 3PVA-(C10)2NaAlg−5Gly, bangta say modelon molekula ya walaan na sankaabebaan a polarisability et 3PVA-(C10)2NaAlg, ya 29.690 Å.
Say impanaral ed saray deskriptor na QSAR et angipatnag ya say istruktura ya mangirerepresenta ed 3PVA-(C10)2NaAlg − 5Gly so sanka-reaktibo parad sankaunaan ya iproproponin pidedeneng.
Parad komaduan paraan na pidedeneng na PVA trimer tan say NaAlg dimer, ipapanengneng na resulta ya saray karga ra et mipara ed saramay niproponin akaunan seksion parad inmunan pidedeneng. Amin ya istruktura et anggapoy electronic charge da, ya mankabaliksan ya amin da et walad ground state.
Unong ed nanengneng ed Table 4, say TDM values ​​(ya kinalkula ed PM6 level) na Term 1 Na Alg − 3PVA-Mid 1 Na Alg et inmatagey manlapud 11.581 Debye ya anggad 15.756, 19.720, 21.756, 22.732, 15.757, 15.757, Na Alg tan Alg −15. Say 3PVA-Mid 1 Na Alg et nanreak ed 1, 2, 3, 4, 5, tan 6 ya yunit na glycerol. Balet, say kabuoan ya enerhiya et onbabawas no ondarakel so bilang na glycerol units, tan no say Term 1 Na Alg − 3PVA- Mid 1 Na Alg et mibabali ed sakey a bilang na glycerol units (1 anggad 6), say kabuoan ya enerhiya et − 996.985, − 1129.013, − 1267, −117, −17. 1418.964, tan − 1637.432 eV, unong ed inkauksoy da.
Parad komaduan probabilidad na pidedeneng, say IP, Log P tan polarizability et nakalkula met ed PM6 ya lebel na teorya. Kanian, inkonsidera ra so taloran sankabiskegan a deskriptor na molecular reactivity. Parad saray istruktura ya mangirerepresenta ed End 1 Na Alg-3PVA-Mid 1 Na Alg ya mibabali ed 1, 2, 3, 4, 5 tan 6 ya yunit na glycerol, say IP et ondarakel manlapud −9.385 eV ya anggad −8.946, −8.848, −8.430, −9.537, −7.99 tan −0.070.07V. Balet, say kinalkula ya Log P value et abeba lapud inplastik na End 1 Na Alg-3PVA-Mid 1 Na Alg ya walay glycerol. No ondarakel so glycerol manlapud 1 anggad 6, say balor to et magmaliw ya -5.334, -6.415, -7.496, -9.096, -9.861 tan -10.53 imbes ya -3.643. Diad kaunoran, say datos na polarizability so angipatnag ya say idarakel na glycerol content et nanresulta ed idakel na polarizability na Term 1 Na Alg- 3PVA- Mid 1 Na Alg. Say polarizability na model molecule ya Term 1 Na Alg- 3PVA- Mid 1 Na Alg et inmatagey manlapud 31.703 Å ya anggad 63.198 Å kayari na impitongtong ed 6 glycerol units. Importante ya imanoen ya say pamarakep ed bilang na glycerol units ed komaduan probability na pidedeneng et gagawaen pian nakumpirma ya anggaman ed karakel na atomo tan komplikadon istruktura, say performance et siansia nin onaaralem no ondarakel so glycerol content. Kanian, nayarin ibaga ya say walan PVA/Na Alg/glycerin model et nayarin onsalat ed saray lithium-ion ya baterya, balet kaukolan ni so mas dakel a panagsukimat tan panagpaalagey.
Say pangibiig ed kapasidad na sakey a tapew ed sakey ya adsorbate tan say pangusisa ed saray nikadkaduman pidedeneng ed baetan na saray sistema et mankaukolan na pikakabat ed klase na pidedeneng ya walad baetan na anggan dinan a duaran atomo, say inkakomplikado na intermolecular tan intramolecular ya pidedeneng, tan say inkaapag-apag na electron density na tapew tan say adsorbent. Say electron density ed bond critical point (BCP) ed baetan na saray mankikimey ya atomo et importante parad pakasuri ed biskeg na bond diad QTAIM analysis. No mas atagey so electron charge density, mas malet so covalent interaction tan, diad inkalapagan, mas atagey so electron density ed sarayan kritikal a punto. Sakey ni, no say total ya electron energy density (H(r)) tan say Laplace charge density (∇2ρ(r)) et abeba nen say 0, saya so mangipapanengneng na kiwawala na covalent (general) ya interaksion. Diad biek a dapag, no say ∇2ρ(r) tan H(r) et mas baleg nen say 0.54, ipapanengneng na satan so kiwawala na aliwan covalent (saradon shell) ya interaksion a singa say makapuy ya hydrogen bonds, van der Waals forces tan electrostatic ya interaksion. Say QTAIM analysis so angipatnag na inkagawa na non-covalent ya interaksion ed saray inaral ya istruktura a singa nanengneng ed Figures 7 tan 8. Base ed analysis, saray model molecules ya mangirerepresenta ed 3PVA − 2Na Alg tan Term 1 Na Alg − 3PVA –Mid 1 Na Alg so angipatnag na mas atagey ya estabilidad nen saray molekula ya mibabali ed nanduruman g units. Saya so lapud pigaran non-covalent ya interaksion ya mas kasmak ed istruktura na alginate a singa say electrostatic ya interaksion tan hydrogen bonds so mamapabiskeg ed alginate ed saray composite. Niarum ni, ipapanengneng na saray resulta mi so kaimportantian na non-covalent ya interaksion ed baetan na 3PVA − 2Na Alg tan Term 1 Na Alg − 3PVA –Mid 1 Na Alg model molecules tan glycine, ya mangipapanengneng ya say glycine et walay importantin betang to ed panguman ed inkalapagan ya electronic environment na saray composite.
QTAIM analysis na model molecule 3PVA − 2NaAlg ya mibabali ed (a) 0 Gly, (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, tan (f) 5Gly.