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Pi tyen lok me jami ma ki lwongo ni sodium, sodium-ion batteries (NIBs) nyutu yoo mukene maber me gwoko teko pa mac. I kare ni, gin ma tye ka gengo dongo pa diro me NIB tye pi peke pa jami ma twero gwoko/gonyo sodium ions pi kare malac. Pi meno, yub me kwan man tye me kwedo adwogi pa medo glycerol i kom polyvinyl alcohol (PVA) ki sodium alginate (NaAlg) ma ki rubu calo jami ma ki lwongo ni NIB electrode. Kwoni man tye ka neno i kom jami ma ki lwongo ni electronic, thermal, ki quantitative structure-activity relationship (QSAR) ma nyutu jami ma ki lwongo ni polymer electrolytes ma jenge i kom PVA, sodium alginate, ki glycerol blends. Jami eni ki kwedo kun kitiyo ki yoo ma ki ngeyo ki yoo ma ki lwongo ni density functional theory (DFT). Kit ma kwedo jami ma ki yubu ni onyutu jami ma mako rwate i kin PVA/alginate ki glycerol, teko me band gap (Eg) ki temo. Adwogi ni nyutu ni medo glycerol kelo dwoko piny wel Eg me 0.2814 eV. Gin ma ki lwongo ni Molecular electrostatic potential surface (MESP) nyutu poko pa kabedo ma tye ki electron madwong ki electron manok ki teko pa molecule i kom electrolyte system ni weny. Gin ma ki kwano ni tye iye enthalpy (H), entropy (ΔS), heat capacity (Cp), Gibbs free energy (G) ki heat of formation. Medo ikom meno, jami mapol ma nyutu kit ma jami tye kwede (QSAR) ma calo wel dipole moment (TDM), wel teko (E), ionization potential (IP), Log P ki polarizability ki kwano i kwan man. Adwogi ni onyutu ni H, ΔS, Cp, G ki TDM omede ki medo rwom me lyeto ki wel glycerol. I kare meno, lyeto me yubu, IP ki E odok piny, ma oweko rwom me tic ki polarizability odoko maber. Medo ikom meno, ka ki medo glycerol, teko pa cell ni omede oo 2.488 V. DFT ki PM6 ma ki kwano ma lubu wel ma lapiny me PVA/Na Alg glycerol-based electrolytes nyutu ni gi twero loko lithium-ion batteries pien tic gi tye mapol, ento medo ki medo ki kwedo ngec mitte.
Kadi bed ni batri ma ki lwongo ni lithium-ion (LIBs) ki tiyo kwede mapol, tic kwede tye ki peko mapol pien kwo ne nok, wel ne lamal, ki peko me gwoke. Bateri ma ki lwongo ni Sodium-ion (SIBs) twero doko gin maber ma ki tiyo kwede me tic ki LIBs pien tye mapol, wel ne lapiny, ki pe kelo peko i kom gin ma ki lwongo ni sodium element. Bateri ma ki lwongo ni Sodium-ion (SIBs) tye ka doko gin ma pire tek me gwoko teko pi jami ma tiyo ki mac1. Bateri ma ki lwongo ni sodium-ion gi jenge i kom electrolytes me konyo tero ion ki kelo teko me mac2,3. Liquid electrolytes pol ne ki yubu ki jami ma ki lwongo ni metal salts ki organic solvents. Tic kwede ma tiyo mito ni ki tam matut i kom ber pa jami ma ki lwongo ni liquid electrolytes, tutwale ka batri ni tye ka nongo peko me lyeto onyo mac4.
Batri ma ki lwongo ni Sodium-ion (SIBs) ki tamo ni obi loko batri ma ki lwongo ni lithium-ion i kare ma cok pien tye ki jami mapol ma ki gwoko i nam, pe kelo two, ki wel jami ma ki tiyo kwede lapiny. Kit ma ki yubu kwede jami ma ki lwongo ni nanomaterials oweko dongo pa jami ma ki gwoko iye ngec, jami ma tiyo ki mac, ki jami ma neno ki wang. Lok mapol ma ki coyo onyutu tic ki jami ma pat pat ma ki lwongo ni nanostructures (me labolle, metal oxides, graphene, nanotubes, ki fullerenes) i sodium-ion batteries. Kwedo ngec ocung i kom yubu jami ma ki lwongo ni anode, medo ki polymers, pi sodium-ion batteries pien gi twero tic i yoo mapol ki gi pe balo kwo pa dano. Miti me kwedo ngec i kom jami ma ki lwongo ni rechargeable polymer battery obi mede labongo akalakala mo. Jami manyen ma ki yubu ki jami ma ki lwongo ni polymer electrode ma tye ki yub ma pat pat ki jami ma pat pat twero yabo yoo pi diro me gwoko teko ma pe balo kwo pa dano. Kadi bed ni jami ma pat pat ma ki lwongo ni polymer electrode ki temo me tic kwede i batri ma ki lwongo ni sodium-ion, dul man pud tye i acaki me dongo ne. Pi batri ma ki lwongo ni sodium-ion, jami mapol ma ki yubu ki polymer ma tye ki kit ma pat pat omyera ki kwan. Malube ki ngec ma wa tye kwede i kare ni i kom kit ma ki gwoko kwede ion me sodium i jami ma ki lwongo ni polymer electrode, ki twero waco ni gurup pa carbonyl, free radicals, ki heteroatoms i yub ma ki keto kacel twero tic calo kabedo ma tiyo pi rwate ki ion me sodium. Pi meno, pire tek me yubu polymer manyen ma tye ki pek pa kabedo ma tiyo ni. Gel polymer electrolyte (GPE) obedo gin ma ki tiyo kwede ma weko batri bedo maber, ion conductivity, pe molo, bedo yot, ki tic maber12.
Polymer matrices tye ki jami ma calo PVA ki polyethylene oxide (PEO)13. Gel permeable polymer (GPE) gengo pii ma tye i polymer matrix, ma dwoko piny peko me mol ka kiporo ki jami ma ki cato14. PVA obedo gin ma ki yubu ma twero balo ne. Tye ki rwom me pii ma malo, wel ne yot ki pe kelo two. Gin ni ki ngeyo pi kit ma en yubu kwede filim, tek ne ki mako ne. En bene tye ki dul ma tiyo (OH) ki rwom me rwate ma malo15,16,17. Rubu polymer, medo plasticizer, medo composite ki in situ polymerization techniques ki tiyo kwede me medo rwom me tic pa PVA-based polymer electrolytes me dwoko piny matrix crystallinity ki medo chain flexibility18,19,20.
Rubu ne obedo yoo ma pire tek me yubu jami ma ki yubu ki jami ma ki lwongo ni polymeric pi tic kwede i gang tic. Polymer ma ki rubu ki tiyo kwede me: (1) medo rom pa polymer ma ki yubu i tic me yubu jami; (2) medo rom pa jami ma ki lwongo ni chemical, physical, ki mechanical jami ma twero balo kom dano; ki (3) rwate ki miti ma tye ka loko oyotoyot pi jami manyen i tic me yubu cam. Ma pe rom ki copolymerization, polymer blending obedo yoo ma wel ne lapiny ma tiyo ki yoo ma yot me kom ma ka tic ki yoo ma tek me nongo jami ma mite21. Me yubu homopolymers, polymers ma pat pat twero tic kacel ki dipole-dipole forces, hydrogen bonds, onyo charge-transfer complexes22,23. Gin ma ki rubu ki jami ma ki yubu ki jami ma ki yubu ki jami ma ki yubu ki jami ma ki yubu twero ribbe maber ki jami ma ki yubu maber, ma miyo gin maber ki wel ma lapiny24,25. Pi meno, tye miti madit me yubu jami ma ki yubu ki jami makwo ma ki lwongo ni polymeric kun ki rubu jami ma ki yubu ki jami ma ki yubu ki dano. PVA ki twero rubu ki sodium alginate (NaAlg), cellulose, chitosan ki starch26.
Sodium alginate obedo gin ma ki lwongo ni polymer ki anionic polysaccharide ma ki kwanyo ki i lum ma ki lwongo ni marine brown algae. Sodium alginate tye ki β-(1-4)-linked D-mannuronic acid (M) ki α-(1-4)-linked L-guluronic acid (G) ma ki yubu i kit ma rwate (poly-M ki poly-G) ki heteropolymeric blocks (MG onyo GM)27. Gin ma tye iye ki rwom me rwate pa M ki G blocks tye ki adwogi ma pire tek i kom kit ma alginate tiyo kwede ki jami ma nen kwede28,29. Sodium alginate ki tiyo kwede i kabedo mapol ki ki kwano pien en twero balo ne, twero tic ki jami makwo, wel ne lapiny, twero yubu filim maber, ki pe kelo two. Ento, wel madwong pa dul ma ki lwongo ni free hydroxyl (OH) ki carboxylate (COO) i dul alginate miyo alginate bedo ma maro pii. Ento, alginate tye ki jami ma tiyo marac pi goro ne ki tek ne. Pi meno, alginate ki twero rubu ki jami mukene ma ki yubu me medo rom pa pii ki kit ma en tiyo kwede30,31.
Mapwod pi ki yubu jami manyen me electrode, kwano DFT pol kare ki tiyo kwede me temo kit ma jami manyen twero bedo kwede. Medo ikom meno, ludiro ikom jami ma kwo tiyo ki jami ma ki lwongo ni molecular modeling me moko ki byeko adwogi me temo, gwoko kare, dwoko piny balo jami ma ki tiyo kwede, ki byeko kit ma jami gi tiiyo kwede32. Molecular modeling odoko dul ma tek ki ma pire tek i dul mapol, medo ki jami ma ki tiyo kwede, nanomaterials, computational chemistry, ki nongo yat33,34. Nong ki tic ki yub me yubu jami, ludiro ikom jami ma kwo twero nongo ngec ma mako jami ma ki lwongo ni molecule, medo ki teko (lyeto me yubu, kero me ionization, teko me tic, ki jami mukene) ki geometry (bond angles, bond lengths, and torsion angles)35. Medo ikom meno, jami ma mako jami ma ki lwongo ni electronic (charge, HOMO ki LUMO band gap energy, electron affinity), jami ma ki lwongo ni spectral (kit me yenge ki teko ma calo FTIR spectra), ki jami ma ki lwongo ni bulk properties (volume, diffusion, viscosity, modulus, etc.)36 ki twero kwano ne.
LiNiPO4 nyutu adwogi maber i pyem ki jami ma ki lwongo ni lithium-ion battery positive electrode materials pi teko ne ma malo (tic ma romo 5.1 V). Me tic ki ber pa LiNiPO4 i kabedo ma tye ki teko madwong, teko ma tiyo omyera ki dwoko piny pien teko ma ki yubu i kare ni twero bedo ma ocung matek i kom teko ma tye piny 4.8 V. Zhang et al. kwedo kit ma ki keto kwede jami ma ki lwongo ni 3d, 4d, ki 5d transition metals i kabedo me Ni pa LiNiPO4, ki yero kit ma ki keto kwede ki tic maber me electrochemical, ki loko teko pa LiNiPO4 kun ki gwoko rwom me tic pa electrochemical ne. Kit ma ki tiyo kwede ma piny loyo ma gunongo obedo 4.21, 3.76, ki 3.5037 pi Ti, Nb, ki Ta-doped LiNiPO4, kit meno.
Pi meno, yub me kwan man tye me kwedo adwogi pa glycerol ma calo gin ma weko jami bedo maber i kom jami ma tiyo ki mac, QSAR ki jami ma mako lyeto pa PVA/NaAlg kun kitiyo ki quantum mechanical calculations pi tic kwede i batri ma ki twero dwoko cen. Kit ma PVA/NaAlg model ki glycerol gi rwate kwede ki kwano kun kitiyo ki Bader's quantum atomic theory of molecules (QTAIM).
Kit ma ki yubu kwede jami ma nyutu kit ma PVA ki NaAlg gi rwate kwede ki glycerol ki yubu kun kitiyo ki DFT. Gin ma ki yubu ni ki kwano kun kitiyo ki jami ma ki lwongo ni Gaussian 0938 software i Spectroscopy Department, National Research Center, Cairo, Egypt. Gin ma ki yubu ni ki yubu maber kun kitiyo ki DFT i B3LYP/6-311G(d, p) level39,40,41,42. Me moko rwate i kin jami ma ki kwano, kwan ma kitimo i rwom acel me rwom me kwan nyutu rwom me geometry ma ki yubu maber. Peko pa frequency ma pe ber i kin frequency ma ki pimo ni nyutu kit ma ki moko kwede i rwom ma lamal ma tye i kom teko ma twero bedo tye. Jami ma nen calo TDM, HOMO/LUMO band gap energy ki MESP ki kwano gi i rwom acel me quantum mechanical me theory. Medo ikom meno, jami mogo ma kwako lyeto calo lyeto me agiki me yubu, teko ma pe ki culu, entropy, enthalpy ki kero me lyeto ki kwano kun kitiyo ki formula ma kimiyo i Table 1. Model ma ki kwano ni ki keto i quantum theory of atoms in molecules (QTAIM) analysis me nongo rwate ma tye ka time i kom jami ma ki kwano. Kwan magi kitimo kun kitiyo ki cik me "output=wfn" i Gaussian 09 software code ki dong ki nyutu kun kitiyo ki Avogadro software code43.
Kan ma E tye teko ma iye, P tye teko, V tye dwonge, Q tye loko lyeto i kin jami ki kabedo ne, T tye rwom me lyeto, ΔH tye alokaloka me enthalpy, ΔG tye alokaloka me teko ma pe ki culu, ΔS tye alokaloka me entropy, a ki b tye rwom me yeng yeng, q tye teko pa atom, ki C tye rwom me electron,445. Me agiki ne, jami ma kit meno ki yubu maber ki QSAR parameters ki kwano i rwom me PM6 kun kitiyo ki SCIGRESS software code46 i Spectroscopy Department me National Research Center i Cairo, Egypt.
I tic wa mukato ni47, wa temo kit ma ki nyutu kwede kit ma PVA adek ki NaAlg aryo gi rwate kwede, ki glycerol ma tiyo calo plasticizer. Kit ma kiloko kwede malo ni, tye yoo aryo ma twero bedo tye pi rwate pa PVA ki NaAlg. Kit aryo ni, ma ki keto ni 3PVA-2Na Alg (ma lubu namba me carbon 10) ki Term 1Na Alg-3PVA-Mid 1Na Alg, tye ki rwom me teko ma nok loyo48 ka kiporo ki jami mukene ma ki keto i tic. Pi meno, adwogi pa medo Gly i kom gin ma ki lwongo ni PVA/Na Alg blend polymer ki temo kun kitiyo ki jami aryo ma lacen: 3PVA-(C10)2Na Alg (ma ki lwongo ni 3PVA-2Na Alg pi bedo yot) ki Term 1 Na Alg − 3PVA-Mid 1 Na Alg. Malube ki lok ma ki coyo, PVA, NaAlg ki glycerol twero yubu hydrogen ma goro i kin dul ma tiyo ki hydroxyl. Kit ma PVA trimer ki NaAlg ki glycerol dimer ni tye ki dul OH mapol, rwate ni twero time ki i kin dul OH acel. cal 1 nyutu rwate pa gin ma ki lwongo ni model glycerol ki model molecule 3PVA-2Na Alg, ki cal 2 nyutu kit ma ki yubu kwede rwate i kin gin ma ki lwongo ni Term 1Na Alg-3PVA-Mid 1Na Alg ki dwong pa glycerol ma pat pat.
Kit ma ki yubu kwede: (a) Gly ki 3PVA − 2Na Alg gi rwate ki (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, ki (f) 5 Gly.
Kit ma ki yubu kwede Term 1Na Alg- 3PVA –Mid 1Na Alg ma tye ka tic ki (a) 1 Gly, (b) 2 Gly, (c) 3 Gly, (d) 4 Gly, (e) 5 Gly, ki (f) 6 Gly.
Teko pa electron band gap obedo gin ma pire tek me neno ka itye ka kwano kit ma jami ma ki lwongo ni electrode tiyo kwede. Pien en tito kit ma electrons gikwo kwede ka jami ni tye ka wok ki alokaloka ma woko. Pi meno, mitte me byeko teko pa electron band gap pa HOMO/LUMO pi jami weny ma ki kwano. Karatac me 2 nyutu alokaloka i teko pa HOMO/LUMO pa 3PVA-(C10)2Na Alg ki Term 1Na Alg − 3PVA- Mid 1Na Alg pi medo glycerol. Malube ki ref47, wel Eg pa 3PVA-(C10)2Na Alg tye 0.2908 eV, kun wel Eg pa dul ma nyutu rwom me rwate me aryo (ie, Term 1Na Alg − 3PVA- Mid 1Na Alg) tye 0.5706 eV.
Ento, kinongo ni medo glycerol okelo alokaloka manok i wel Eg pa 3PVA-(C10)2Na Alg. Ka 3PVA-(C10)2NaAlg orwate ki 1, 2, 3, 4 ki 5 glycerol units, wel Eg ne odoko 0.302, 0.299, 0.308, 0.289 ki 0.281 eV, kit meno. Ento, tye ngec ma pire tek ni inge medo 3 glycerol units, wel Eg odoko nok loyo pa 3PVA-(C10)2Na Alg. Labol ma nyutu rwate pa 3PVA-(C10)2Na Alg ki glycerol units abic en aye labol ma twero rwate. Man tere ni ka wel glycerol units tye ka mede, rwom me rwate bene tye ka mede.
I kare meno, pi tyen lok me aryo me rwate, teko pa HOMO/LUMO pa molecule ma ki nyutu ma nyutu Term 1Na Alg − 3PVA –Mid 1Na Alg- 1Gly, Term 1Na Alg − 3PVA –Mid 1Na Alg- 2Gly, Term 1Na Alg − 3PVA – 1Na Alg- 1Gly, Term 1Na Algly Alg − 3PVA –Mid 1Na Alg- 4Gly, Term 1Na Alg − 3PVA –Mid 1Na Alg- 5Gly ki Term 1Na Alg − 3PVA –Mid 1Na Alg- 6Gly dugu 1.343, 1.34 7, 0.976, 0.607, 0.048, ki V kit meno. Karatac me 2 nyutu rwom me HOMO/LUMO band gap ma ki kwano pi jami weny ma ki yubu. Medo ikom meno, kit ma kit meno pa dul mukwongo ni ki dwoko cen kany.
Lok me band i kom jami ma ki lwongo ni solid state physics waco ni ka band gap pa gin ma ki lwongo ni electrode odok piny, teko pa electrode me gin ni mede. Doping obedo yoo ma pol kare kitiyo kwede me dwoko piny band gap pa jami ma ki lwongo ni sodium-ion cathode. Jiang ki luwote otiiyo ki Cu doping me medo rwom me tic pa jami ma ki lwongo ni β-NaMnO2. Nono ki kwano DFT, gin onongo ni keto jami ma ki keto i kom jami ni odwoko piny band gap pa jami ni ki i 0.7 eV nio wa i 0.3 eV. Man nyutu ni keto Cu medo rwom me tic pa jami ma ki lwongo ni β-NaMnO2.
MESP ki gonyo ni calo teko ma rwate i kin rwom me teko pa molecule ki teko acel ma tye maber. MESP ki ngeyo calo gin ma tiyo maber me niang ki gonyo kit ma jami ma ki yubu ki jami ma ki lwongo ni chemical ki kit ma gi loko kwede. MESP ki tiyo kwede me niang kit ma jami ma ki lwongo ni polymeric gi rwate kwede. MESP tito kit ma ki poko kwede teko i kom gin ma ki kwano ni. Medo ikom meno, MESP miyo ngec ikom kabedo ma tye ka tic ikom jami ma ki kwano32. cal me 3 nyutu MESP pa 3PVA-(C10) 2Na Alg, 3PVA-(C10) 2Na Alg − 1Gly, 3PVA-(C10) 2Na Alg − 2Gly, 3PVA-(C10) 2Na Alg − 3Gly, 3PVA-(C10) 2Na Alg − 2Gly, ki Algly 3PVA-(C10) 2Na Alg − 5Gly ma ki byeko i B3LYP/6-311G(d, p) rwom me lok.
MESP ma ki kwano ki B3LYP/6-311 g(d, p) pi (a) Gly ki 3PVA − 2Na Alg ma tye ka tic ki (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, ki (f) 5 Gly.
I kare meno, cal. 4 nyutu adwogi ma ki kwano me MESP pi 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 PVA – Mid 1Gly, Term 1Na Alg-3PVA – Mid 1Na Alg − 4Gly, Term 1Na Alg- 3PVA – Mid 1Na Alg- 5gly ki Term 1Na Alg-3PVA – Mid 1Na Alg − 6Gly, kit meno. MESP ma ki kwano ni ki nyutu calo kit ma ki nyutu kwede. Lain ma ki lwongo ni contour ni ki nyutu ki kala ma pat pat. Kala acel acel nyutu wel ma pat pat me electronegativity. Kala makwar nyutu kabedo ma tye ki electronegative onyo reactive. I kare meno, kala ma yellow nyutu kabedo ma pe rwate 49, 50, 51 i yub ni. Adwogi me MESP onyutu ni tic pa 3PVA-(C10)2Na Alg omede ki medo kala makwar i kom jami ma ki kwano. I kare meno, rangi makwar ma tye i MESP map me Term 1Na Alg-3PVA – Mid 1Na Alg model molecule dwoko piny pi rwate ki jami ma pat pat ma tye i glycerol. Aloka loka i poko rangi makwar i kom yub ma ki yubu ni nyutu kit ma jami ni tiyo kwede, kun medo rwom me tic ni moko medo pa electronegativity pa 3PVA-(C10)2Na Alg model molecule pi medo pa glycerol.
B3LYP/6-311 g(d, p) ki kwano MESP Term pa 1Na Alg-3PVA-Mid 1Na Alg ma tye ka tic ki (a) 1 Gly, (b) 2 Gly, (c) 3 Gly, (d) 4 Gly, (e) 5 Gly, ki (f) 6 Gly.
Jami ma ki yubu ni weng tye ki rwom me lyeto ma calo enthalpy, entropy, kero me lyeto, teko ma pe ki culu ki lyeto me yubu ma ki kwano i rwom me lyeto ma pat pat ma tye i kin 200 K nio wa i 500 K. Me tito kit ma jami ma nen, medo i kom kwan kit ma gi tiyo kwede, mitte bene me kwano kit ma lyeto gi tiyo kwede macalo tic pa rwom me lyeto, ma twero bedo pi rwate pa ngat acel acel ki kwano kun kitiyo ki equation ma kimiyo i Table 1. Kwan me rwom me lyeto magi kitero calo lanyut ma pire tek me gamo ki cung matek pa jami ma kit meno i rwom me lyeto mapat pat.
Kit ma enthalpy pa PVA trimer, en mukwongo rwate ki NaAlg dimer, lacen ki i dul OH ma ki keto i carbon atom #10, ki dong i agiki ki glycerol. Enthalpy obedo rwom me teko ma tye i yub me thermodynamic. Enthalpy rom ki lyeto weny ma tye i gin moni, ma rom ki teko ma tye i gin moni ka i medo ki wel ma ki nongo ki i kom dwonge ki teko ne. I lok mukene, enthalpy nyutu wel lyeto ki tic ma ki medo onyo ki kwanyo ki ikom gin moni52.
cal me 5 nyutu alokaloka me enthalpy i kare me tic pa 3PVA-(C10)2Na Alg ki rwom me glycerol ma pat pat. Nying ma ki coyo ma ki lwongo ni A0, A1, A2, A3, A4, ki A5 nyutu jami ma ki lwongo ni 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, ki 3PVA-(C10)2Na Alg − 5Gly, kit meno. cal 5a nyutu ni enthalpy mede ki medo rwom me lyeto ki wel glycerol. Enthalpy pa gin ma nyutu 3PVA-(C10)2NaAlg − 5Gly (ie, A5) i 200 K tye 27.966 cal/mol, kun enthalpy pa gin ma nyutu 3PVA- 2NaAlg i 200 K tye 13.490 cal/mol. Me agiki ne, kit ma enthalpy ni tye maber, lok man tye endothermic.
Entropy ki gonyo ni calo gin ma ki pimo teko ma pe tye i yub me thermodynamic ma ki umu ki pol kare ki ngeyo ni obedo gin ma ki pimo me peko ma tye i yub ni. cal 5b nyutu alokaloka i entropy pa 3PVA-(C10)2NaAlg ki rwom me lyeto ki kit ma en rwate kwede ki dul glycerol ma pat pat. Gin ma ki nyutu ni nyutu ni entropy loko kit ma rwom me lyeto mede kwede ki 200 K me oo 500 K. cal 5b nyutu ni entropy pa 3PVA-(C10)2Na Alg model ni cito 200 cal/K/mol i 200 K pien 3PVA-(C10)2Na Alg model ni nyutu lattice lattice. Ka lyeto tye ka mede, 3PVA-(C10)2Na Alg model ni doko goro ki tito medo pa entropy ka lyeto tye ka mede. Medo ikom meno, nen maber ni kit ma 3PVA-C10 2Na Alg- 5 Gly tye kwede tye ki wel ma malo loyo.
Kit ma kit meno bene ki neno i cal 5c, ma nyutu alokaloka i kero me lyeto ki rwom me lyeto. Kit me lyeto obedo wel lyeto ma mite me loko lyeto pa gin moni ki 1 °C47. cal 5c nyutu alokaloka i kero me lyeto pa gin ma ki lwongo ni model molecule 3PVA-(C10)2NaAlg pi rwate ki 1, 2, 3, 4, ki 5 glycerol units. cal ni nyutu ni kero me lyeto pa gin ma ki lwongo ni 3PVA-(C10)2NaAlg mede ki rwom me lyeto. Medo pa kero me lyeto ma ki neno ki rwom me lyeto ma tye ka mede ni oa ki i yeng pa yamo ma ki lwongo ni phonon. Medo ikom meno, tye lanyut ma nyutu ni medo wel glycerol kelo medo kero me lyeto pa model 3PVA-(C10)2NaAlg. Medo ikom meno, kit ma ki yubu kwede nyutu ni 3PVA-(C10)2NaAlg−5Gly tye ki kero me lyeto ma malo loyo ka kiporo ki kit ma ki yubu kwede mukene.
Jami mukene ma calo teko ma pe ki culu ki lyeto me agiki me yubu ki kwano pi jami ma ki kwano ki ki nyutu gi i cal 5d ki e, kit meno. Lyeto me agiki me yubu obedo lyeto ma ki gonyo onyo ki kwanyo i kare me yubu gin mo maleng ki i kom jami ma tye iye i te teko ma pe loko. Guvu ma pe ki culu ki twero gonyo ni calo gin ma rom ki guvu, ma calo, wel ne cung i kom wel gin ma tye i rwom me thermodynamic acel acel. Teko ma pe ki culu ki lyeto me yubu 3PVA-(C10)2NaAlg−5Gly onwongo tye piny loyo ki onwongo tye -1318.338 ki -1628.154 kcal/mol, kit meno. Ka i poro, dul ma nyutu 3PVA-(C10)2NaAlg tye ki teko ma malo ki lyeto me yubu -690.340 ki -830.673 kcal/mol, kit meno, ka kiporo ki dul mukene. Kit ma ki nyutu kwede i cal 5, rwom me lyeto ma pat pat gi loko pi rwate ki glycerol. Teko pa Gibbs ma pe ki culu tye marac, ma nyutu ni yub ma ki yubu ni tye ma ocung matek.
PM6 okwano rwom me lyeto pa 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), ki 3PVA- (C10) 2Na Alg − 5 Gly (model A5), kan ma (a) tye enthalpy, (b) entropy, (c) kero me lyeto, (d) teko ma pe ki culu, ki (e) lyeto me yubu.
Ki tung cing kany, kit me rwate me aryo i kin PVA trimer ki dimeric NaAlg time i agiki ki dul OH ma tye i kin PVA trimer structure. Ma calo i dul mukwongo, rwom me lyeto ki kwano kun kitiyo ki rwom me lok acel. cal 6a-e nyutu apoka poka pa enthalpy, entropy, kero me lyeto, teko ma pe ki culu ki, me agiki, lyeto me yubu. cal 6a-c nyutu ni enthalpy, entropy ki kero me lyeto pa Term 1 NaAlg-3PVA-Mid 1 NaAlg nyutu kit acel ki gurup mukwongo ka gi rwate ki 1, 2, 3, 4, 5 ki 6 glycerol units. Medo ikom meno, wel gi mede mot mot ka lyeto tye ka mede. Medo ikom meno, i Term 1 Na Alg − 3PVA-Mid 1 Na Alg ma ki yubu, wel enthalpy, entropy ki kero me lyeto omede ki medo pa glycerol. Coc ma ki coyo ma ki lwongo ni B0, B1, B2, B3, B4, B5 ki B6 nyutu jami ma lubo ni: 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- 1 Na Alg- 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 ki Term 1 Na Alg- 3PVA- Mid 1 Na Alg − 6 Gly. Kit ma ki nyutu kwede i cal 6a-c, nen maber ni wel pa enthalpy, entropy ki kero me lyeto mede ka wel glycerol units mede ki 1 nio wa i 6.
PM6 okwano rwom me lyeto pa 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) 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), ki Term 1 Na Alg- 3PVA- Mid 1 Na Alg – 6 Gly (model B5), medo ki enpy (model B), entropy, (c) kero me lyeto, (d) teko ma pe ki culu, ki (e) lyeto me yubu.
Medo ikom meno, yub ma nyutu Term 1 Na Alg- 3PVA- Mid 1 Na Alg- 6 Gly tye ki wel ma malo me enthalpy, entropy ki kero me lyeto ka kiporo ki yub mukene. I kin gii, wel gi omede ki 16.703 cal/mol, 257.990 cal/mol/K ki 131.323 kcal/mol i Term 1 Na Alg − 3PVA- Mid 1 Na Alg me oo 33.223 cal/mol, 420.038 cal/mol/mol/kl i Term 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly, kit meno.
Ento, cal 6d ki e nyutu rwom me lyeto pa teko ma pe ki culu ki lyeto me agiki me yubu (HF). HF ki twero gonyo ni calo alokaloka me enthalpy ma time ka mole acel me gin moni ki yubu ki i kom jami ma tye iye i te cik ma rwate. Man nen ki i cal ni teko ma pe ki culu ki lyeto me agiki me yubu jami ma ki kwano ni nyutu rwom me lyeto, ma calo, gi mede mot mot ki rwom me lyeto ma mede. Medo ikom meno, cal ni bene moko ni dul ma nyutu Term 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly tye ki teko ma lapiny loyo ki HF ma lapiny loyo. Jami aryo ni weng odok piny ki -758.337 me oo -899.741 K cal/mol i kare me 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly me oo -1,476.591 ki -1,828.523 K cal/mol. Tye ka nen ki i adwogi ni HF dwoko piny ki medo pa glycerol units. Man tere ni pi medo pa dul ma tiyo, rwom me tic bene mede ki dong teko manok ma mite me timo tic ni. Man moko ni PVA/NaAlg ma ki yubu ki jami ma ki lwongo ni plasticized ki tiyo kwede i batri pi teko ne ma lamal.
I kom lok, adwogi me lyeto ki poko i dul aryo: adwogi me lyeto ma piny ki adwogi me lyeto ma malo. Adwogi pa lyeto ma piny pol kare ki winyo i lobo ma tye i latitude ma malo, calo Greenland, Canada, ki Russia. I kare me ngiico, lyeto pa yamo ma woko i kabedo eni tye piny ki diguri Celsius. Kwo ki tic pa batri ma ki lwongo ni lithium-ion twero bedo marac pi lyeto ma piny, tutwal ma ki tiyo kwede i motoka ma tiyo ki mac, motoka ma tiyo ki mac, ki motoka ma tiyo ki mac. Wot i dan polo obedo kabedo mukene ma ngiic ma mito batri ma ki lwongo ni lithium-ion. Me labolle, lyeto i kom lobo Mars twero poto piny nio wa i -120 degrees Celsius, ma kelo peko madit i tic ki batri ma ki lwongo ni lithium-ion i yamo. Lyeto ma piny twero kelo dwoko piny i rwom me cwalo mac ki tic pa jami ma ki lwongo ni lithium-ion batteries, ma kelo dwoko piny i rwom me nya pa lithium ions i electrode ki ionic conductivity i electrolyte. Balo man kelo dwoko piny teko ki teko, ki i kare mukene bene dwoko piny tic53.
Adwogi me lyeto ma malo time i kabedo mapol ma ki tiyo kwede, medo ki kabedo ma lyet ki piny, kun adwogi me lyeto ma piny ni pol ne tye i kabedo ma lyet manok. Adwogi me lyeto ma piny ki nongo ki i lyeto ma tye i kin piny, kun adwogi me lyeto ma malo pol kare ki nongo ki i lyeto ma malo ma tye i batri me lithium-ion i kare me tic.
Batri ma ki lwongo ni Lithium-ion kelo lyeto i te rwom ma malo (ma tye iye keto mac oyot ki kwanyo mac oyot), ma weko lyeto ma iye mede. Bedo i lyeto ma malo bene twero balo tic pa batri, medo ki rwenyo kero ki teko. Pol kare, rwenyo pa lithium ki dwoko jami ma tiyo i lyeto ma malo kelo rwenyo kero, ki rwenyo teko ni oa ki i medo teko ma tye iye. Ka lyeto okato woko, lyeto bino, ma i kare mogo twero kelo lyeto ma oyot oyot onyo bene wango.
Kwano QSAR obedo yoo me kwano wel ma ki tiyo kwede me nongo wat ma tye i kin tic pa jami makwo ki kit ma kom gi nen kwede. Jami weny ma ki yubu ni ki yubu maber ki jami mogo ma ki lwongo ni QSAR ki kwano i rwom me PM6. Karatac me 3 nyutu jami mogo ma ki kwano ma nyutu QSAR. Labol pa jami ma ki nyutu ni tye teko, TDM, teko weny (E), kero me ionization (IP), Log P, ki polarizability (nen Table 1 pi formula me moko IP ki Log P).
Adwogi me cura ni nyutu ni wel kero pa jami ma ki kwano ni weng tye zero pien gi tye i rwom ma piny. Pi tyen lok me rwate mukwongo, TDM pa glycerol onwongo tye 2.788 Debye ki 6.840 Debye pi 3PVA-(C10) 2Na Alg, kun wel TDM onwongo omede nio wa i 17.990 Debye, 8.848 Debye, 5.874 Debye, 7.658 Debye ki Debye ka 7.77.77. 3PVA-(C10) 2Na Alg otiiyo ki 1, 2, 3, 4 ki 5 unit me glycerol, kit meno. Ka wel TDM tye malo, ci rwom me tic ne ki jami ma orumowa bene tye malo.
Guvu weny (E) bene ki kwano, ki wel E pa glycerol ki 3PVA-(C10)2 NaAlg kinongo ni tye -141.833 eV ki -200092.503 eV, kit meno. I kare meno, jami ma nyutu 3PVA-(C10)2 NaAlg gi rwate ki 1, 2, 3, 4 ki 5 glycerol units; E doko -996.837, -1108.440, -1238.740, -1372.075 ki -1548.031 eV, kit meno. Medo gin ma ki lwongo ni glycerol weko teko ma tye iye dwoko piny ki dong medo rwom me tic. Malube ki wel teko ma ki kwano, ki moko ni molecule ma ki nyutu ni, ma tye 3PVA-2Na Alg-5 Gly, tye ki teko madwong loyo molecule mukene ma ki nyutu ni. Gin ma time ni kubbe ki kit ma gi nen kwede. 3PVA-(C10)2NaAlg tye ki dul -COONa aryo keken, kun jami mukene ni tye ki dul -COONa aryo ento gi tye ki dul OH mapol, ma nyutu ni tic gi i kom piny tye ka mede.
Medo ikom meno, teko me ionization (IE) pa jami weny ma ki yubu ni ki keto i kwan man. Teko me ionization obedo gin ma pire tek me pimo kit ma gin ma ki kwano ni tiyo kwede. Teko ma mite me tero electron ki i kom molecule acel me cito i kabedo ma pe gik ki lwongo ni teko me ionization. Nyutu rwom me ionization (ma en aye reactivity) pa molecule. Ka teko me ionization tye malo, ci reactivity bene bedo piny. Adwogi me IE pa 3PVA-(C10)2NaAlg ma tye ka tic ki 1, 2, 3, 4 ki 5 glycerol units onwongo tye -9.256, -9.393, -9.393, -9.248 ki -9.323 eV, kit meno, kun IEs pa glycerol ki 3.323 eV ki -9.341 eV, kit meno. Kit ma medo glycerol okelo dwoko piny i wel IP, rwom me tic pa molecule omede, ma medo tic pa PVA/NaAlg/glycerol model molecule i jami ma tiyo ki mac.
Labol me abic i Table 3 tye Log P, ma en aye logarithm me poko kin jami ma ki tiyo kwede me tito ka ce dul ma ki kwano ni tye ma maro pii onyo pe maro pii. Labol me Log P ma pe ber nyutu ni molecule ma maro pii, ma tere ni romo mol oyotoyot i pii ki mol marac i jami ma kwo. wel maber nyutu gin ma tye ka time ma pat.
Malube ki adwogi ma kinongo, ki twero waco ni jami weny ma ki yubu ni gi maro pii, pien rwom me Log P gi tye (3PVA-(C10)2Na Alg − 1Gly, 3PVA-(C10)2Na Alg − 2Gly, 3PVA-(C10)2Na Alg − 3Gly, PVA-(C10)2Na Alg − 3Gly(C10) 4Gly ki 3PVA-(C10)2Na Alg − 5Gly) tye -3.537, -5.261, -6.342, -7.423 ki -8.504, kit meno, kun rwom me Log P pa glycerol tye -1.081 keken ki 3PVA-(C10)2Na Alg tye -1010 keken. Man tere ni kit pa gin ma ki kwano ni obi loko ka jami ma ki lwongo ni molecules me pii ki keto i yub ne.
Me agiki ne, rwom me apoka poka pa jami weny ki kwano i rwom me PM6 kun kitiyo ki yoo ma ki ngeyo. Onwongo ki waco ni kit ma jami mapol twero poko kwede jami cung i kom jami mapol. Gin ma pire tek loyo tye dit pa gedo ma kitye ka kwano ne. Pi jami weny ma tye ki kit me acel me rwate i kin 3PVA ki 2NaAlg (rwate ni time ki ikom atom me carbon namba 10), polarizability ni ki medo ki medo glycerol. Polarizability ni mede ki 29.690 Å me oo 35.076, 40.665, 45.177, 50.239 ki 54.638 Å pi rwate ki 1, 2, 3, 4 ki 5 glycerol units. Pi meno, kinongo ni gin ma ki lwongo ni model molecule ma tye ki polarizability ma malo loyo tye 3PVA-(C10)2NaAlg−5Gly, kun model molecule ma tye ki polarizability ma lapiny loyo tye 3PVA-(C10)2NaAlg, ma tye 29.690 Å.
Kwedo lok ma mako QSAR onyutu ni kit ma ki yubu kwede 3PVA-(C10)2NaAlg − 5Gly aye ma tiyo matek pi rwate mukwongo ma ki waco ni.
Pi kit me rwate me aryo i kin PVA trimer ki NaAlg dimer, adwogi ni nyutu ni wel gi rom ki ma ki waco i dul mukato pi rwate mukwongo. Jami weny ma ki gedo ni tye ki mac ma pe ki teko, ma nyutu ni gin weng tye i ngom.
Kit ma ki nyutu kwede i Table 4, wel TDM (ma ki kwano i rwom me PM6) pa Term 1 Na Alg - 3PVA-Mid 1 Na Alg omede ki 11.581 Debye me oo 15.756, 19.720, 21.756, 22.732, 15.720, 15.757, ki Alg −15. 3PVA-Mid 1 Na Alg otiiyo ki 1, 2, 3, 4, 5, ki 6 unit me glycerol. Ento, teko weng dwoko piny ka wel glycerol units omede, ki ka Term 1 Na Alg − 3PVA- Mid 1 Na Alg orwate ki wel glycerol units mo (1 onyo 6), teko weng tye − 996.985, − 1129.013, − 1267, −113, −17. 1418.964, ki - 1637.432 eV, kit meno.
Pi rwom me rwate me aryo, IP, Log P ki polarizability bene ki kwano i rwom me PM6 me lok. Pi meno, gin gu tamo i kom jami adek ma tek loyo ma nyutu kit ma jami ma ki lwongo ni molecule gi loko kwede. Pi jami ma ki yubu ma nyutu agiki 1 Na Alg-3PVA-Mid 1 Na Alg ma tye ka tic ki 1, 2, 3, 4, 5 ki 6 glycerol units, IP mede ki −9.385 eV me oo −8.946, −8.848, −8.430, −9.537, −7.999 ki −0.070. Ento, wel ma ki kwano me Log P onwongo tye piny pi loko pa End 1 Na Alg-3PVA-Mid 1 Na Alg ki glycerol. Ka wel glycerol tye ka mede ki 1 me oo 6, wel ne doko -5.334, -6.415, -7.496, -9.096, -9.861 ki -10.53 ma ka -3.643. Me agiki ne, ngec ma ki nongo ki ikom polarizability onyutu ni medo glycerol ma tye iye okelo medo polarizability pa Term 1 Na Alg- 3PVA- Mid 1 Na Alg. Polarizability pa molecule ma ki yubu ni Term 1 Na Alg- 3PVA- Mid 1 Na Alg omede ki 31.703 Å me oo 63.198 Å inge rwate ki 6 glycerol units. Pire tek me ngeyo ni medo wel glycerol units i rwom me rwate me aryo ni ki tiimo me moko ni kede wel atoms madwong ki kit ma gi nen kwede, tic ne pud tye ka mede ki medo wel glycerol. Pi meno, ki twero waco ni PVA/Na Alg/glycerin ma tye ni twero loko batri ma ki lwongo ni lithium-ion, ento mitte ni ki med kwan ki dongo ne.
Nyutu kit ma gin moni twero mako kwede gin ma ki lwongo ni adsorbate ki neno kit ma jami ni gikubbe kwede mito ngec i kom kit ma gi rwate kwede i kin atom aryo mo keken, kit ma rwate kwede i kin molecular ki intramolecular, ki kit ma electron density ma tye i kom gin moni ki gin ma ki lwongo ni adsorbent gi poko kwede. Pek pa electron i kabedo ma pire tek (BCP) i kin atom ma gi rwate pire tek me temo teko me rwate i QTAIM analysis. Ka dwong pa electron tye malo, ci rwate pa covalent bedo maber ki, i kom lok, dwong pa electron bedo malo i kabedo ma pire tek ni. Medo ikom meno, ka wel teko pa electron (H(r)) ki Laplace charge density (∇2ρ(r)) tye ma nok loyo 0, man nyutu ni tye covalent (ma rwate) ma rwate. Ki tung cing kany, ka ∇2ρ(r) ki H(r) dit kato 0.54, man nyutu ni tye jami ma pe rwate (ma ki umu) ma calo hydrogen bonds ma goro, van der Waals forces ki electrostatic interactions. Kwano QTAIM onyutu kit ma jami ma pe rwate i kin jami ma ki kwano ni kit ma ki nyutu kwede i cal 7 ki 8. Malube ki kwano, jami ma ki nyutu ma nyutu 3PVA − 2Na Alg ki Term 1 Na Alg − 3PVA –Mid 1 Na Alg onyutu rwom ma malo loyo jami ma gi rwate ki g units ma pat pat. Man tye pien wel jami ma pe rwate ma tye i dul pa alginate calo jami ma mako mac ki hydrogen bonds miyo alginate twero gwoko jami ma ki rubu ni. Medo ikom meno, adwogi wa nyutu teko pa rwate ma pe rwate i kin 3PVA − 2Na Alg ki Term 1 Na Alg − 3PVA –Mid 1 Na Alg ma ki yubu ki glycine, ma nyutu ni glycine tye ki tic ma pire tek me loko kit ma jami ni tye kwede.
QTAIM nyamo gin ma ki lwongo ni model molecule 3PVA − 2NaAlg ma tye ka tic ki (a) 0 Gly, (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, ki (f) 5Gly.