Ua tsaug rau koj tuaj xyuas nature.com. Lub browser version uas koj siv muaj kev txhawb nqa CSS tsawg. Rau qhov kev paub zoo tshaj plaws, peb xav kom siv lub browser version tshiab tshaj plaws (lossis tua hom kev sib raug zoo hauv Internet Explorer). Tsis tas li ntawd, txhawm rau kom ntseeg tau tias muaj kev txhawb nqa txuas ntxiv, lub xaib no yuav tsis suav nrog cov qauv lossis JavaScript.
Vim muaj sodium ntau heev, cov roj teeb sodium-ion (NIBs) yog lwm txoj hauv kev zoo rau kev khaws cia lub zog electrochemical. Tam sim no, qhov teeb meem tseem ceeb hauv kev txhim kho NIB thev naus laus zis yog qhov tsis muaj cov khoom siv electrode uas tuaj yeem khaws cia / tso tawm sodium ions ntev. Yog li ntawd, lub hom phiaj ntawm txoj kev tshawb fawb no yog los tshawb nrhiav qhov cuam tshuam ntawm kev ntxiv glycerol rau polyvinyl cawv (PVA) thiab sodium alginate (NaAlg) sib xyaw ua cov khoom siv electrode NIB. Txoj kev tshawb fawb no tsom mus rau kev piav qhia txog hluav taws xob, thermal, thiab quantitative structure-activity relationship (QSAR) ntawm polymer electrolytes raws li PVA, sodium alginate, thiab glycerol sib xyaw. Cov khoom no raug tshawb nrhiav siv cov txheej txheem semi-empirical thiab density functional theory (DFT). Txij li thaum kev tshuaj xyuas cov qauv qhia txog cov ntsiab lus ntawm kev sib cuam tshuam ntawm PVA / alginate thiab glycerol, lub zog sib txawv ntawm cov qhab (Eg) tau tshawb nrhiav. Cov txiaj ntsig qhia tau tias kev ntxiv glycerol ua rau tus nqi Eg txo qis rau 0.2814 eV. Qhov chaw muaj peev xwm ntawm cov electrostatic molecular (MESP) qhia txog kev faib tawm ntawm cov cheeb tsam uas muaj electron ntau thiab cov cheeb tsam uas tsis muaj electron ntau thiab cov nqi molecular hauv tag nrho cov electrolyte system. Cov kev ntsuas thermal uas tau kawm suav nrog enthalpy (H), entropy (ΔS), peev xwm kub (Cp), Gibbs free energy (G) thiab cua sov ntawm kev tsim. Tsis tas li ntawd, ntau cov lus piav qhia txog kev sib raug zoo ntawm cov qauv thiab kev ua ub no (QSAR) xws li tag nrho dipole moment (TDM), tag nrho lub zog (E), ionization potential (IP), Log P thiab polarizability tau tshawb xyuas hauv kev tshawb fawb no. Cov txiaj ntsig tau qhia tias H, ΔS, Cp, G thiab TDM nce nrog rau qhov kub thiab txias thiab cov ntsiab lus glycerol nce ntxiv. Lub caij no, qhov cua sov ntawm kev tsim, IP thiab E txo qis, uas ua rau cov tshuaj tiv thaiv thiab polarizability zoo dua. Tsis tas li ntawd, los ntawm kev ntxiv glycerol, lub zog ntawm lub cell nce mus txog 2.488 V. Kev suav DFT thiab PM6 raws li cov electrolytes PVA/Na Alg glycerol-based uas pheej yig qhia tau tias lawv tuaj yeem hloov cov roj teeb lithium-ion ib feem vim lawv muaj ntau yam kev ua haujlwm, tab sis xav tau kev txhim kho thiab kev tshawb fawb ntxiv.
Txawm hais tias cov roj teeb lithium-ion (LIBs) siv dav dav, lawv daim ntawv thov ntsib ntau qhov kev txwv vim lawv lub neej luv luv, tus nqi siab, thiab kev txhawj xeeb txog kev nyab xeeb. Cov roj teeb Sodium-ion (SIBs) yuav dhau los ua lwm txoj hauv kev rau LIBs vim lawv muaj ntau, tus nqi qis, thiab tsis muaj tshuaj lom ntawm cov khoom sodium. Cov roj teeb Sodium-ion (SIBs) tab tom dhau los ua lub zog khaws cia tseem ceeb rau cov khoom siv hluav taws xob1. Cov roj teeb Sodium-ion vam khom ntau rau electrolytes los pab txhawb kev thauj mus los ion thiab tsim hluav taws xob2,3. Cov electrolytes kua feem ntau yog tsim los ntawm cov ntsev hlau thiab cov kuab tshuaj organic. Cov ntawv thov siv tau yuav tsum tau xav txog kev nyab xeeb ntawm cov electrolytes kua, tshwj xeeb tshaj yog thaum lub roj teeb raug kev ntxhov siab thermal lossis hluav taws xob4.
Cov roj teeb Sodium-ion (SIBs) yuav hloov cov roj teeb lithium-ion yav tom ntej vim lawv muaj ntau yam khoom siv hauv dej hiav txwv, tsis muaj tshuaj lom, thiab tus nqi khoom qis. Kev tsim cov khoom siv nanomaterials tau ua kom nrawm dua kev tsim cov ntaub ntawv khaws cia, cov khoom siv hluav taws xob, thiab cov khoom siv kho qhov muag. Ib lub cev loj ntawm cov ntaub ntawv tau ua pov thawj txog kev siv ntau yam nanostructures (piv txwv li, hlau oxides, graphene, nanotubes, thiab fullerenes) hauv cov roj teeb sodium-ion. Kev tshawb fawb tau tsom mus rau kev tsim cov ntaub ntawv anode, suav nrog cov polymers, rau cov roj teeb sodium-ion vim lawv qhov kev hloov pauv thiab kev phooj ywg ib puag ncig. Kev txaus siab rau kev tshawb fawb hauv thaj chaw ntawm cov roj teeb polymer rechargeable yuav nce ntxiv. Cov ntaub ntawv polymer electrode tshiab nrog cov qauv thiab cov khoom tshwj xeeb yuav ua rau txoj hauv kev rau cov thev naus laus zis khaws cia lub zog zoo rau ib puag ncig. Txawm hais tias ntau yam ntaub ntawv polymer electrode tau tshawb nrhiav rau kev siv hauv cov roj teeb sodium-ion, thaj chaw no tseem nyob rau theem pib ntawm kev txhim kho. Rau cov roj teeb sodium-ion, ntau cov ntaub ntawv polymer nrog cov qauv sib txawv yuav tsum tau tshawb nrhiav. Raws li peb cov kev paub tam sim no ntawm cov txheej txheem khaws cia ntawm sodium ions hauv cov ntaub ntawv polymer electrode, nws tuaj yeem xav tias cov pab pawg carbonyl, cov dawb radicals, thiab heteroatoms hauv lub kaw lus sib txuas tuaj yeem ua haujlwm ua qhov chaw nquag rau kev sib cuam tshuam nrog sodium ions. Yog li ntawd, nws yog qhov tseem ceeb rau kev tsim cov polymers tshiab nrog qhov ceev ntawm cov chaw nquag no. Gel polymer electrolyte (GPE) yog lwm txoj hauv kev thev naus laus zis uas txhim kho kev ntseeg siab ntawm lub roj teeb, ion conductivity, tsis muaj to, siab yooj ywm, thiab kev ua tau zoo zoo12.
Cov polymer matrices muaj xws li cov ntaub ntawv xws li PVA thiab polyethylene oxide (PEO)13. Gel permeable polymer (GPE) immobilizes cov kua electrolyte hauv polymer matrix, uas txo qhov kev pheej hmoo ntawm kev xau piv rau cov neeg sib cais lag luam14. PVA yog cov polymer biodegradable synthetic. Nws muaj qhov permittivity siab, pheej yig thiab tsis muaj tshuaj lom. Cov khoom siv no paub txog nws cov khoom ua yeeb yaj kiab, kev ruaj khov tshuaj lom neeg thiab kev nplaum. Nws kuj muaj cov pab pawg ua haujlwm (OH) thiab qhov ceev ceev ntawm kev sib txuas cross-linking15,16,17. Polymer blending, plasticizer ntxiv, composite ntxiv thiab cov txheej txheem polymerization hauv situ tau siv los txhim kho qhov conductivity ntawm PVA-based polymer electrolytes kom txo cov matrix crystallinity thiab ua kom cov saw hlau yooj ywm18,19,20.
Kev sib xyaw ua ke yog ib txoj hauv kev tseem ceeb rau kev tsim cov ntaub ntawv polymeric rau kev siv hauv kev lag luam. Cov polymer sib xyaw feem ntau siv los: (1) txhim kho cov khoom ua tiav ntawm cov polymers ntuj hauv kev siv hauv kev lag luam; (2) txhim kho cov tshuaj lom neeg, lub cev, thiab cov khoom siv kho tshuab ntawm cov ntaub ntawv biodegradable; thiab (3) hloov kho rau qhov kev thov hloov pauv sai rau cov ntaub ntawv tshiab hauv kev lag luam ntim khoom noj. Tsis zoo li copolymerization, polymer blending yog ib qho txheej txheem pheej yig uas siv cov txheej txheem lub cev yooj yim dua li cov txheej txheem tshuaj lom neeg nyuaj kom ua tiav cov khoom xav tau21. Txhawm rau tsim cov homopolymers, cov polymers sib txawv tuaj yeem sib cuam tshuam los ntawm dipole-dipole forces, hydrogen bonds, lossis charge-transfer complexes22,23. Cov sib xyaw ua los ntawm cov polymers ntuj thiab hluavtaws tuaj yeem sib xyaw ua ke zoo biocompatibility nrog cov khoom siv kho tshuab zoo heev, tsim cov khoom zoo dua ntawm tus nqi tsim khoom qis24,25. Yog li ntawd, muaj kev txaus siab heev rau kev tsim cov ntaub ntawv polymeric biorelevant los ntawm kev sib xyaw cov polymers hluavtaws thiab ntuj. PVA tuaj yeem sib xyaw nrog sodium alginate (NaAlg), cellulose, chitosan thiab starch26.
Sodium alginate yog ib qho polymer ntuj thiab anionic polysaccharide rho tawm los ntawm marine brown algae. Sodium alginate muaj β-(1-4)-linked D-mannuronic acid (M) thiab α-(1-4)-linked L-guluronic acid (G) uas tau teeb tsa ua homopolymers (poly-M thiab poly-G) thiab heteropolymers blocks (MG lossis GM)27. Cov ntsiab lus thiab qhov sib piv ntawm M thiab G blocks muaj qhov cuam tshuam loj rau cov khoom siv tshuaj lom neeg thiab lub cev ntawm alginate28,29. Sodium alginate yog siv dav thiab kawm vim nws biodegradability, biocompatibility, pheej yig, cov khoom zoo-tsim zaj duab xis, thiab tsis muaj tshuaj lom. Txawm li cas los xij, ntau pawg hydroxyl dawb (OH) thiab carboxylate (COO) hauv cov saw hlau alginate ua rau alginate hydrophilic heev. Txawm li cas los xij, alginate muaj cov khoom siv tsis zoo vim nws qhov brittleness thiab rigidity. Yog li ntawd, alginate tuaj yeem ua ke nrog lwm cov khoom siv hluavtaws los txhim kho kev nkag siab dej thiab cov khoom siv kho tshuab30,31.
Ua ntej tsim cov khoom siv electrode tshiab, kev suav DFT feem ntau siv los ntsuas qhov ua tau ntawm cov khoom siv tshiab. Tsis tas li ntawd, cov kws tshawb fawb siv cov qauv molecular los lees paub thiab kwv yees cov txiaj ntsig sim, txuag lub sijhawm, txo cov tshuaj pov tseg, thiab kwv yees tus cwj pwm sib cuam tshuam32. Kev ua qauv molecular tau dhau los ua ib ceg tseem ceeb thiab tseem ceeb ntawm kev tshawb fawb hauv ntau qhov chaw, suav nrog cov ntaub ntawv tshawb fawb, nanomaterials, computational chemistry, thiab kev tshawb pom tshuaj33,34. Siv cov kev pab cuam qauv, cov kws tshawb fawb tuaj yeem tau txais cov ntaub ntawv molecular ncaj qha, suav nrog lub zog (kub ntawm kev tsim, ionization potential, activation energy, thiab lwm yam) thiab geometry (bond angles, bond lengths, thiab torsion angles)35. Tsis tas li ntawd, cov khoom siv hluav taws xob (charge, HOMO thiab LUMO band gap energy, electron affinity), spectral properties (charging vibrational modes thiab intensities xws li FTIR spectra), thiab bulk properties (volume, diffusion, viscosity, modulus, thiab lwm yam)36 tuaj yeem suav tau.
LiNiPO4 qhia tau tias muaj peev xwm zoo dua hauv kev sib tw nrog cov khoom siv electrode zoo ntawm lithium-ion roj teeb vim nws lub zog ceev ceev (qhov hluav taws xob ua haujlwm ntawm kwv yees li 5.1 V). Yuav kom siv tau qhov zoo ntawm LiNiPO4 hauv thaj chaw muaj hluav taws xob siab, qhov hluav taws xob ua haujlwm yuav tsum tau txo qis vim tias cov electrolyte hluav taws xob siab uas tam sim no tsim tau tsuas yog nyob ruaj khov ntawm qhov hluav taws xob qis dua 4.8 V. Zhang et al. tau tshawb nrhiav qhov doping ntawm txhua cov hlau hloov pauv 3d, 4d, thiab 5d hauv qhov chaw Ni ntawm LiNiPO4, xaiv cov qauv doping nrog kev ua tau zoo electrochemical zoo heev, thiab kho qhov hluav taws xob ua haujlwm ntawm LiNiPO4 thaum tswj hwm qhov ruaj khov ntawm nws cov kev ua tau zoo electrochemical. Qhov hluav taws xob ua haujlwm qis tshaj plaws uas lawv tau txais yog 4.21, 3.76, thiab 3.5037 rau Ti, Nb, thiab Ta-doped LiNiPO4, raws li.
Yog li ntawd, lub hom phiaj ntawm txoj kev tshawb fawb no yog los tshawb nrhiav txog qhov cuam tshuam ntawm glycerol ua tus neeg ua kom cov yas lo rau cov khoom siv hluav taws xob, QSAR descriptors thiab thermal properties ntawm PVA/NaAlg system siv cov kev suav quantum mechanical rau nws daim ntawv thov hauv cov roj teeb ion-ion rechargeable. Kev sib cuam tshuam molecular ntawm PVA/NaAlg qauv thiab glycerol tau raug tshuaj xyuas siv Bader's quantum atomic theory of molecules (QTAIM).
Ib qho qauv molecule uas sawv cev rau kev sib cuam tshuam ntawm PVA nrog NaAlg thiab tom qab ntawd nrog glycerol tau raug kho kom zoo siv DFT. Tus qauv tau suav los ntawm kev siv Gaussian 0938 software ntawm Spectroscopy Department, National Research Center, Cairo, Egypt. Cov qauv tau raug kho kom zoo siv DFT ntawm B3LYP / 6-311G (d, p) theem 39,40,41,42. Txhawm rau txheeb xyuas qhov kev sib cuam tshuam ntawm cov qauv kawm, kev tshawb fawb zaus ua ntawm tib theem ntawm kev tshawb fawb qhia txog kev ruaj khov ntawm cov geometry zoo tshaj plaws. Qhov tsis muaj cov zaus tsis zoo ntawm txhua qhov zaus ntsuas tau qhia txog cov qauv inferred hauv qhov tseeb zoo minima ntawm qhov chaw muaj peev xwm zog. Cov yam ntxwv lub cev xws li TDM, HOMO / LUMO band gap zog thiab MESP tau raug suav los ntawm tib theem quantum mechanical ntawm kev tshawb fawb. Ntxiv rau, qee qhov kev ntsuas kub xws li qhov kub kawg ntawm kev tsim, lub zog dawb, entropy, enthalpy thiab lub peev xwm kub tau suav los ntawm kev siv cov qauv uas tau muab rau hauv Rooj 1. Cov qauv kawm tau raug rau kev tshuaj xyuas quantum theory of atoms in molecules (QTAIM) txhawm rau txheeb xyuas cov kev sib cuam tshuam uas tshwm sim ntawm qhov chaw ntawm cov qauv kawm. Cov kev suav no tau ua tiav los ntawm kev siv cov lus txib "output = wfn" hauv Gaussian 09 software code thiab tom qab ntawd pom siv Avogadro software code43.
Qhov twg E yog lub zog sab hauv, P yog lub siab, V yog qhov ntim, Q yog qhov sib pauv cua sov ntawm lub kaw lus thiab nws ib puag ncig, T yog qhov kub thiab txias, ΔH yog qhov hloov pauv enthalpy, ΔG yog qhov hloov pauv zog dawb, ΔS yog qhov hloov pauv entropy, a thiab b yog cov kev co, q yog tus nqi atomic, thiab C yog qhov ceev ntawm atomic electron 44,45. Thaum kawg, cov qauv zoo sib xws tau raug kho kom zoo thiab cov kev ntsuas QSAR tau suav ntawm PM6 qib siv SCIGRESS software code46 ntawm Spectroscopy Department ntawm National Research Center hauv Cairo, Egypt.
Hauv peb txoj haujlwm yav dhau los47, peb tau soj ntsuam qhov qauv zoo tshaj plaws uas piav qhia txog kev sib cuam tshuam ntawm peb chav PVA nrog ob chav NaAlg, nrog glycerol ua haujlwm ua tus yas. Raws li tau hais los saum toj no, muaj ob qho kev ua tau rau kev sib cuam tshuam ntawm PVA thiab NaAlg. Ob lub qauv, xaiv 3PVA-2Na Alg (raws li tus lej carbon 10) thiab Lub Sijhawm 1Na Alg-3PVA-Mid 1Na Alg, muaj qhov sib txawv zog me tshaj plaws48 piv rau lwm cov qauv uas tau xav txog. Yog li ntawd, qhov cuam tshuam ntawm Gly ntxiv rau qhov qauv zoo tshaj plaws ntawm PVA/Na Alg sib xyaw polymer tau tshawb xyuas siv ob lub qauv tom kawg: 3PVA-(C10)2Na Alg (hu ua 3PVA-2Na Alg rau kev yooj yim) thiab Lub Sijhawm 1 Na Alg − 3PVA-Mid 1 Na Alg. Raws li cov ntaub ntawv, PVA, NaAlg thiab glycerol tuaj yeem tsim cov hydrogen bonds tsis muaj zog ntawm cov pab pawg hydroxyl functional. Vim tias ob qho tib si PVA trimer thiab NaAlg thiab glycerol dimer muaj ntau pawg OH, qhov kev sib cuag tuaj yeem ua tiav los ntawm ib qho ntawm OH pawg. Daim duab 1 qhia txog kev sib cuam tshuam ntawm tus qauv glycerol molecule thiab tus qauv molecule 3PVA-2Na Alg, thiab Daim duab 2 qhia txog tus qauv tsim ntawm kev sib cuam tshuam ntawm tus qauv molecule Term 1Na Alg-3PVA-Mid 1Na Alg thiab ntau yam concentration ntawm glycerol.
Cov qauv zoo tshaj plaws: (a) Gly thiab 3PVA − 2Na Alg sib cuam tshuam nrog (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, thiab (f) 5 Gly.
Cov qauv zoo tshaj plaws ntawm Term 1Na Alg-3PVA –Mid 1Na Alg cuam tshuam nrog (a) 1 Gly, (b) 2 Gly, (c) 3 Gly, (d) 4 Gly, (e) 5 Gly, thiab (f) 6 Gly.
Lub zog sib txawv ntawm cov electron band yog ib qho tseem ceeb uas yuav tsum xav txog thaum kawm txog qhov ua haujlwm ntawm cov khoom siv electrode. Vim nws piav qhia txog tus cwj pwm ntawm cov electrons thaum cov khoom siv raug kev hloov pauv sab nraud. Yog li ntawd, nws yog qhov tsim nyog los kwv yees lub zog sib txawv ntawm cov electron band ntawm HOMO / LUMO rau txhua qhov qauv uas tau kawm. Rooj 2 qhia txog kev hloov pauv hauv HOMO / LUMO zog ntawm 3PVA- (C10) 2Na Alg thiab Term 1Na Alg − 3PVA- Mid 1Na Alg vim yog ntxiv glycerol. Raws li ref47, tus nqi Eg ntawm 3PVA- (C10) 2Na Alg yog 0.2908 eV, thaum tus nqi Eg ntawm cov qauv uas cuam tshuam txog qhov muaj feem ntawm kev sib cuam tshuam thib ob (piv txwv li, Term 1Na Alg − 3PVA- Mid 1Na Alg) yog 0.5706 eV.
Txawm li cas los xij, nws tau pom tias qhov ntxiv ntawm glycerol ua rau muaj kev hloov pauv me ntsis hauv tus nqi Eg ntawm 3PVA-(C10)2Na Alg. Thaum 3PVA-(C10)2NaAlg cuam tshuam nrog 1, 2, 3, 4 thiab 5 glycerol units, nws cov nqi Eg tau dhau los ua 0.302, 0.299, 0.308, 0.289 thiab 0.281 eV, feem. Txawm li cas los xij, muaj kev nkag siab zoo uas tom qab ntxiv 3 glycerol units, tus nqi Eg tau dhau los ua me dua li ntawm 3PVA-(C10)2Na Alg. Tus qauv sawv cev rau kev sib cuam tshuam ntawm 3PVA-(C10)2Na Alg nrog tsib glycerol units yog tus qauv sib cuam tshuam feem ntau. Qhov no txhais tau tias thaum tus lej ntawm glycerol units nce ntxiv, qhov feem pua ​​ntawm kev sib cuam tshuam kuj nce ntxiv.
Lub caij no, rau qhov thib ob qhov tshwm sim ntawm kev sib cuam tshuam, lub zog HOMO/LUMO ntawm cov qauv molecules sawv cev rau Lub Sijhawm 1Na Alg − 3PVA –Mid 1Na Alg- 1Gly, Lub Sijhawm 1Na Alg − 3PVA –Mid 1Na Alg- 2Gly, Lub Sijhawm 1Na Alg − 3PVA –Mid 1Na Alg- 3Gly, Lub Sijhawm 1Na Alg − 3PVA –Mid 1Na Alg- 4Gly, Lub Sijhawm 1Na Alg − 3PVA –Mid 1Na Alg- 5Gly thiab Lub Sijhawm 1Na Alg − 3PVA –Mid 1Na Alg- 6Gly dhau los ua 1.343, 1.34 7, 0.976, 0.607, 0.348 thiab 0.496 eV, raws li. Rooj 2 qhia txog lub zog sib txawv HOMO/LUMO uas tau xam rau txhua qhov qauv. Ntxiv mus, tib tus cwj pwm ntawm kev sib cuam tshuam ntawm thawj pawg tau rov ua dua ntawm no.
Lub tswv yim band hauv solid state physics hais tias thaum qhov sib txawv ntawm cov khoom siv electrode txo qis, qhov hluav taws xob conductivity ntawm cov khoom siv nce ntxiv. Doping yog ib txoj hauv kev siv ntau los txo qhov sib txawv ntawm cov khoom siv sodium-ion cathode. Jiang et al. siv Cu doping los txhim kho qhov hluav taws xob conductivity ntawm β-NaMnO2 layered cov ntaub ntawv. Siv DFT xam, lawv pom tias doping txo qhov sib txawv ntawm cov khoom siv los ntawm 0.7 eV mus rau 0.3 eV. Qhov no qhia tau hais tias Cu doping txhim kho qhov hluav taws xob conductivity ntawm β-NaMnO2 cov ntaub ntawv.
MESP yog txhais tias yog lub zog sib cuam tshuam ntawm kev faib cov nqi molecular thiab ib qho nqi zoo. MESP yog suav tias yog ib qho cuab yeej zoo rau kev nkag siab thiab txhais cov khoom siv tshuaj lom neeg thiab kev ua haujlwm. MESP tuaj yeem siv los nkag siab txog cov txheej txheem ntawm kev sib cuam tshuam ntawm cov ntaub ntawv polymeric. MESP piav qhia txog kev faib cov nqi hauv cov tshuaj uas raug kawm. Tsis tas li ntawd, MESP muab cov ntaub ntawv hais txog cov chaw nquag hauv cov ntaub ntawv uas raug kawm32. Daim duab 3 qhia cov phiaj xwm MESP ntawm 3PVA-(C10) 2Na Alg, 3PVA-(C10) 2Na Alg − 1Gly, 3PVA-(C10) 2Na Alg − 2Gly, 3PVA-(C10) 2Na Alg − 3Gly, 3PVA-(C10) 2Na Alg − 4Gly, thiab 3PVA-(C10) 2Na Alg − 5Gly kwv yees ntawm B3LYP/6-311G(d, p) theem ntawm kev xav.
MESP cov duab kos tau xam nrog B3LYP/6-311 g(d, p) rau (a) Gly thiab 3PVA − 2Na Alg cuam tshuam nrog (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, thiab (f) 5 Gly.
Lub sijhawm no, daim duab 4 qhia txog cov txiaj ntsig xam tau ntawm MESP rau Lub Sijhawm 1Na Alg-3PVA – Mid 1Na Alg, Lub Sijhawm 1Na Alg-3PVA – Mid 1Na Alg-1Gly, Lub Sijhawm 1Na Alg-3PVA – Mid 1Na Alg − 2Gly, Lub Sijhawm 1Na Alg-3PVA – Mid 1Na Alg − 3gly, Lub Sijhawm 1Na Alg-3PVA – Mid 1Na Alg − 4Gly, Lub Sijhawm 1Na Alg-3PVA – Mid 1Na Alg-5gly thiab Lub Sijhawm 1Na Alg-3PVA – Mid 1Na Alg − 6Gly, raws li. MESP xam tau sawv cev ua tus cwj pwm contour. Cov kab contour tau sawv cev los ntawm cov xim sib txawv. Txhua xim sawv cev rau tus nqi electronegativity sib txawv. Xim liab qhia txog cov chaw electronegative lossis reactive heev. Lub sijhawm no, xim daj sawv cev rau cov chaw nruab nrab 49, 50, 51 hauv cov qauv. Cov txiaj ntsig MESP qhia tau hais tias qhov kev ua haujlwm ntawm 3PVA-(C10)2Na Alg nce ntxiv nrog rau qhov nce ntawm cov xim liab nyob ib puag ncig cov qauv kawm. Lub caij no, qhov xim liab nyob rau hauv daim ntawv qhia MESP ntawm Term 1Na Alg-3PVA – Mid 1Na Alg qauv molecule txo qis vim yog kev sib cuam tshuam nrog cov ntsiab lus glycerol sib txawv. Qhov kev hloov pauv ntawm kev faib xim liab nyob ib puag ncig cov qauv uas tau thov qhia txog qhov kev ua haujlwm, thaum qhov kev nce ntxiv ntawm qhov kev lees paub qhov kev nce ntawm electronegativity ntawm 3PVA-(C10)2Na Alg qauv molecule vim yog qhov nce ntawm cov ntsiab lus glycerol.
B3LYP/6-311 g(d, p) xam MESP Term ntawm 1Na Alg-3PVA-Mid 1Na Alg cuam tshuam nrog (a) 1 Gly, (b) 2 Gly, (c) 3 Gly, (d) 4 Gly, (e) 5 Gly, thiab (f) 6 Gly.
Txhua cov qauv uas tau muab tso tawm muaj lawv cov kev ntsuas kub xws li enthalpy, entropy, peev xwm kub, lub zog dawb thiab cua sov ntawm kev tsim uas tau xam ntawm qhov kub sib txawv hauv qhov ntau ntawm 200 K txog 500 K. Txhawm rau piav qhia txog tus cwj pwm ntawm cov kab ke lub cev, ntxiv rau kev kawm txog lawv tus cwj pwm hluav taws xob, nws tseem tsim nyog los kawm txog lawv tus cwj pwm thermal ua ib qho haujlwm ntawm qhov kub vim lawv sib cuam tshuam nrog ib leeg, uas tuaj yeem suav nrog siv cov qauv uas tau muab hauv Rooj 1. Kev kawm txog cov kev ntsuas kub no suav hais tias yog ib qho cim qhia tseem ceeb ntawm kev teb thiab kev ruaj khov ntawm cov kab ke lub cev ntawm qhov kub sib txawv.
Raws li qhov enthalpy ntawm PVA trimer, nws thawj zaug cuam tshuam nrog NaAlg dimer, tom qab ntawd los ntawm OH pawg txuas nrog carbon atom # 10, thiab thaum kawg nrog glycerol. Enthalpy yog qhov ntsuas ntawm lub zog hauv lub thermodynamic system. Enthalpy yog sib npaug rau tag nrho cov cua sov hauv ib lub system, uas yog sib npaug rau lub zog sab hauv ntawm lub system ntxiv rau cov khoom ntawm nws qhov ntim thiab siab. Hauv lwm lo lus, enthalpy qhia ntau npaum li cas cua sov thiab ua haujlwm ntxiv rau lossis tshem tawm ntawm cov tshuaj 52.
Daim Duab 5 qhia txog kev hloov pauv enthalpy thaum lub sijhawm ua haujlwm ntawm 3PVA-(C10)2Na Alg nrog cov glycerol sib txawv. Cov ntawv luv A0, A1, A2, A3, A4, thiab A5 sawv cev rau cov qauv molecules 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, thiab 3PVA-(C10)2Na Alg − 5Gly, raws li. Daim Duab 5a qhia tias enthalpy nce nrog rau qhov kub thiab cov ntsiab lus glycerol nce ntxiv. Lub enthalpy ntawm cov qauv uas sawv cev rau 3PVA-(C10)2NaAlg − 5Gly (piv txwv li, A5) ntawm 200 K yog 27.966 cal/mol, thaum lub enthalpy ntawm cov qauv uas sawv cev rau 3PVA-2NaAlg ntawm 200 K yog 13.490 cal/mol. Thaum kawg, txij li thaum lub enthalpy yog qhov zoo, qhov kev tshuaj tiv thaiv no yog endothermic.
Entropy yog txhais tias yog kev ntsuas ntawm lub zog tsis muaj nyob rau hauv lub kaw lus thermodynamic kaw thiab feem ntau suav hais tias yog kev ntsuas ntawm qhov tsis sib haum xeeb ntawm lub kaw lus. Daim duab 5b qhia txog kev hloov pauv ntawm entropy ntawm 3PVA-(C10)2NaAlg nrog qhov kub thiab nws cuam tshuam li cas nrog cov chav glycerol sib txawv. Daim duab qhia tau hais tias entropy hloov pauv linearly thaum qhov kub nce ntawm 200 K txog 500 K. Daim duab 5b qhia meej meej tias entropy ntawm 3PVA-(C10)2Na Alg qauv feem ntau yog 200 cal/K/mol ntawm 200 K vim tias 3PVA-(C10)2Na Alg qauv qhia txog kev tsis sib haum xeeb tsawg dua. Thaum qhov kub nce, 3PVA-(C10)2Na Alg qauv dhau los ua kev tsis sib haum xeeb thiab piav qhia txog kev nce hauv entropy nrog qhov kub nce. Ntxiv mus, nws yog qhov tseeb tias cov qauv ntawm 3PVA-C10 2Na Alg-5Gly muaj tus nqi entropy siab tshaj plaws.
Tus cwj pwm zoo ib yam li no tau pom hauv Daim Duab 5c, uas qhia txog kev hloov pauv ntawm lub peev xwm cua sov nrog qhov kub thiab txias. Lub peev xwm cua sov yog qhov ntau ntawm cov cua sov uas xav tau los hloov qhov kub thiab txias ntawm ib qho khoom los ntawm 1 ° C47. Daim Duab 5c qhia txog kev hloov pauv ntawm lub peev xwm cua sov ntawm tus qauv molecule 3PVA-(C10)2NaAlg vim muaj kev sib cuam tshuam nrog 1, 2, 3, 4, thiab 5 glycerol units. Daim duab qhia tau hais tias lub peev xwm cua sov ntawm tus qauv 3PVA-(C10)2NaAlg nce linearly nrog qhov kub thiab txias. Qhov kev nce ntxiv ntawm lub peev xwm cua sov nrog qhov kub thiab txias nce yog vim phonon thermal vibrations. Tsis tas li ntawd, muaj pov thawj tias kev nce ntxiv ntawm cov ntsiab lus glycerol ua rau muaj kev nce ntxiv ntawm lub peev xwm cua sov ntawm tus qauv 3PVA-(C10)2NaAlg. Tsis tas li ntawd, cov qauv qhia tau hais tias 3PVA-(C10)2NaAlg−5Gly muaj qhov muaj peev xwm cua sov siab tshaj plaws piv rau lwm cov qauv.
Lwm cov kev ntsuas xws li lub zog dawb thiab qhov kub kawg ntawm kev tsim tau suav rau cov qauv kawm thiab tau qhia hauv Daim Duab 5d thiab e, raws li. Qhov kub kawg ntawm kev tsim yog qhov kub tso tawm lossis nqus thaum lub sijhawm tsim cov khoom ntshiab los ntawm nws cov khoom sib xyaw hauv qab qhov siab tas li. Lub zog dawb tuaj yeem txhais tau tias yog cov khoom zoo ib yam li lub zog, piv txwv li, nws tus nqi nyob ntawm qhov ntau ntawm cov khoom hauv txhua lub xeev thermodynamic. Lub zog dawb thiab cua sov ntawm kev tsim ntawm 3PVA-(C10)2NaAlg−5Gly yog qhov qis tshaj plaws thiab yog -1318.338 thiab -1628.154 kcal / mol, raws li. Hauv kev sib piv, cov qauv sawv cev rau 3PVA-(C10)2NaAlg muaj lub zog dawb siab tshaj plaws thiab cua sov ntawm kev tsim cov nqi ntawm -690.340 thiab -830.673 kcal / mol, raws li, piv rau lwm cov qauv. Raws li tau pom hauv Daim Duab 5, ntau yam khoom thermal tau hloov pauv vim yog kev cuam tshuam nrog glycerol. Lub zog Gibbs dawb yog qhov tsis zoo, qhia tias cov qauv tau thov ruaj khov.
PM6 tau xam cov thermal parameters ntawm cov ntshiab 3PVA- (C10) 2Na Alg (qauv A0), 3PVA- (C10) 2Na Alg − 1 Gly (qauv A1), 3PVA- (C10) 2Na Alg − 2 Gly (qauv A2), 3PVA- (C10) 2Na Alg − 3 Gly (qauv A3), 3PVA- (C10) 2Na Alg − 4 Gly (qauv A4), thiab 3PVA- (C10) 2Na Alg − 5 Gly (qauv A5), qhov twg (a) yog enthalpy, (b) entropy, (c) peev xwm cua sov, (d) lub zog dawb, thiab (e) cua sov ntawm kev tsim.
Ntawm qhov tod tes, hom kev sib cuam tshuam thib ob ntawm PVA trimer thiab dimeric NaAlg tshwm sim hauv cov davhlau ya nyob twg thiab nruab nrab OH pawg hauv PVA trimer qauv. Ib yam li hauv thawj pawg, cov txheej txheem thermal tau suav siv tib theem ntawm kev xav. Daim duab 6a-e qhia txog kev hloov pauv ntawm enthalpy, entropy, peev xwm kub, lub zog dawb thiab, thaum kawg, cua sov ntawm kev tsim. Daim duab 6a-c qhia tias enthalpy, entropy thiab peev xwm kub ntawm Lub Sijhawm 1 NaAlg-3PVA-Mid 1 NaAlg qhia txog tus cwj pwm zoo ib yam li thawj pawg thaum cuam tshuam nrog 1, 2, 3, 4, 5 thiab 6 glycerol units. Ntxiv mus, lawv cov nqi maj mam nce nrog qhov kub thiab txias nce. Tsis tas li ntawd, hauv daim ntawv thov Lub Sijhawm 1 Na Alg − 3PVA-Mid 1 Na Alg qauv, cov nqi enthalpy, entropy thiab peev xwm kub nce nrog qhov nce ntawm glycerol cov ntsiab lus. Cov lus luv B0, B1, B2, B3, B4, B5 thiab B6 sawv cev rau cov qauv hauv qab no: Lub Sijhawm 1 Na Alg − 3PVA- Mid 1 Na Alg, Lub Sijhawm 1 Na Alg- 3PVA- Mid 1 Na Alg − 1 Gly, Lub Sijhawm 1 Na Alg- 3PVA- Mid 1 Na Alg − 2gly, Lub Sijhawm 1 Na Alg- 3PVA- Mid 1 Na Alg − 3gly, Lub Sijhawm 1 Na Alg- 3PVA- Mid 1 Na Alg − 4 Gly, Lub Sijhawm 1 Na Alg- 3PVA- Mid 1 Na Alg − 5 Gly thiab Lub Sijhawm 1 Na Alg- 3PVA- Mid 1 Na Alg − 6 Gly. Raws li pom hauv daim duab 6a-c, nws yog qhov tseeb tias cov nqi ntawm enthalpy, entropy thiab lub peev xwm cua sov nce ntxiv thaum tus lej ntawm glycerol units nce ntxiv ntawm 1 mus rau 6.
PM6 tau xam cov thermal parameters ntawm lub sijhawm ntshiab 1 Na Alg-3PVA-Mid 1 Na Alg (qauv B0), Lub sijhawm 1 Na Alg-3PVA-Mid 1 Na Alg – 1 Gly (qauv B1), Lub sijhawm 1 Na Alg-3PVA-Mid 1 Na Alg – 2 Gly (qauv B2), Lub sijhawm 1 Na Alg-3PVA-Mid 1 Na Alg – 3 Gly (qauv B3), Lub sijhawm 1 Na Alg-3PVA-Mid 1 Na Alg – 4 Gly (qauv B4), Lub sijhawm 1 Na Alg-3PVA-Mid 1 Na Alg – 5 Gly (qauv B5), thiab Lub sijhawm 1 Na Alg-3PVA-Mid 1 Na Alg – 6 Gly (qauv B6), suav nrog (a) enthalpy, (b) entropy, (c) peev xwm cua sov, (d) lub zog dawb, thiab (e) cua sov ntawm kev tsim.
Ntxiv rau, cov qauv uas sawv cev rau Lub Sijhawm 1 Na Alg- 3PVA- Mid 1 Na Alg- 6 Gly muaj cov nqi siab tshaj plaws ntawm enthalpy, entropy thiab lub peev xwm cua sov piv rau lwm cov qauv. Ntawm lawv, lawv cov nqi nce ntxiv los ntawm 16.703 cal/mol, 257.990 cal/mol/K thiab 131.323 kcal/mol hauv Lub Sijhawm 1 Na Alg − 3PVA- Mid 1 Na Alg mus rau 33.223 cal/mol, 420.038 cal/mol/K thiab 275.923 kcal/mol hauv Lub Sijhawm 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly, feem.
Txawm li cas los xij, Cov Duab 6d thiab e qhia txog qhov kub thiab txias nyob ntawm lub zog dawb thiab qhov kub kawg ntawm kev tsim (HF). HF tuaj yeem txhais tau tias yog qhov hloov pauv enthalpy uas tshwm sim thaum ib mole ntawm ib yam khoom raug tsim los ntawm nws cov ntsiab lus nyob rau hauv cov xwm txheej ntuj thiab tus qauv. Nws yog qhov tseeb los ntawm daim duab tias lub zog dawb thiab qhov kub kawg ntawm kev tsim ntawm tag nrho cov qauv kawm qhia txog kev vam khom linear rau qhov kub thiab txias, piv txwv li, lawv maj mam thiab linearly nce nrog qhov kub thiab txias nce. Tsis tas li ntawd, daim duab kuj tau lees paub tias cov qauv sawv cev rau Lub Sijhawm 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly muaj lub zog dawb qis tshaj plaws thiab HF qis tshaj plaws. Ob qho tib si parameter txo qis los ntawm -758.337 mus rau -899.741 K cal/mol hauv lub sijhawm 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly mus rau -1,476.591 thiab -1,828.523 K cal/mol. Nws yog qhov tseeb los ntawm cov txiaj ntsig tias HF ​​​tsawg zuj zus nrog rau kev nce ntawm glycerol units. Qhov no txhais tau tias vim yog kev nce ntawm cov pab pawg ua haujlwm, qhov kev ua haujlwm kuj nce ntxiv thiab yog li ntawd tsawg dua lub zog xav tau los ua qhov kev ua haujlwm. Qhov no lees paub tias cov yas PVA / NaAlg tuaj yeem siv rau hauv cov roj teeb vim nws qhov kev ua haujlwm siab.
Feem ntau, cov teebmeem kub tau muab faib ua ob hom: cov teebmeem kub qis thiab cov teebmeem kub siab. Cov teebmeem ntawm qhov kub qis feem ntau hnov ​​​​​​nyob rau hauv cov tebchaws nyob rau ntawm qhov siab latitudes, xws li Greenland, Canada, thiab Russia. Thaum lub caij ntuj no, qhov kub sab nraud ntawm cov chaw no yog qis dua xoom degrees Celsius. Lub neej thiab kev ua tau zoo ntawm cov roj teeb lithium-ion tuaj yeem cuam tshuam los ntawm qhov kub qis, tshwj xeeb tshaj yog cov uas siv hauv cov tsheb fais fab hybrid plug-in, cov tsheb fais fab ntshiab, thiab cov tsheb fais fab hybrid. Kev mus ncig hauv qhov chaw yog lwm qhov chaw txias uas xav tau cov roj teeb lithium-ion. Piv txwv li, qhov kub ntawm Mars tuaj yeem poob rau -120 degrees Celsius, uas ua rau muaj kev cuam tshuam loj rau kev siv cov roj teeb lithium-ion hauv spacecraft. Qhov kub ua haujlwm qis tuaj yeem ua rau txo qis ntawm tus nqi hloov pauv thiab kev ua haujlwm tshuaj lom neeg ntawm cov roj teeb lithium-ion, ua rau txo qis ntawm tus nqi diffusion ntawm lithium ions hauv electrode thiab ionic conductivity hauv electrolyte. Qhov kev puas tsuaj no ua rau muaj peev xwm thiab lub zog txo qis, thiab qee zaum txawm tias txo qis kev ua tau zoo53.
Qhov kub siab tshwm sim hauv ntau qhov chaw siv, suav nrog qhov kub siab thiab qis, thaum qhov kub qis feem ntau tsuas yog txwv rau qhov kub qis xwb. Qhov kub qis feem ntau yog txiav txim siab los ntawm qhov kub ib puag ncig, thaum qhov kub siab feem ntau yog qhov tseeb dua rau qhov kub siab hauv lub roj teeb lithium-ion thaum lub sijhawm ua haujlwm.
Cov roj teeb lithium-ion tsim cua sov nyob rau hauv cov xwm txheej tam sim no siab (xws li them sai thiab tso tawm sai), uas ua rau qhov kub sab hauv nce siab. Kev raug rau qhov kub siab kuj tseem tuaj yeem ua rau lub roj teeb ua haujlwm poob qis, suav nrog kev poob peev xwm thiab lub zog. Feem ntau, kev poob ntawm lithium thiab kev rov qab los ntawm cov khoom siv nquag ntawm qhov kub siab ua rau muaj peev xwm poob, thiab kev poob fais fab yog vim muaj kev tiv thaiv sab hauv nce ntxiv. Yog tias qhov kub tsis tswj tau, kev khiav tawm ntawm thermal tshwm sim, uas qee zaum tuaj yeem ua rau muaj kev kub hnyiab lossis txawm tias tawg.
Kev suav QSAR yog ib txoj kev suav lej lossis kev ua lej siv los txheeb xyuas kev sib raug zoo ntawm kev ua haujlwm ntawm lub cev thiab cov khoom ntawm cov tshuaj. Tag nrho cov molecule tsim tau raug kho kom zoo thiab qee cov khoom QSAR tau raug suav ntawm qib PM6. Rooj 3 teev qee cov lus piav qhia QSAR uas tau suav. Piv txwv ntawm cov lus piav qhia no yog them, TDM, tag nrho lub zog (E), ionization potential (IP), Log P, thiab polarizability (saib Rooj 1 rau cov qauv los txiav txim siab IP thiab Log P).
Cov txiaj ntsig ntawm kev xam qhia tau hais tias tag nrho cov nqi ntawm tag nrho cov qauv kawm yog xoom vim lawv nyob hauv lub xeev av. Rau qhov tshwm sim thawj zaug ntawm kev sib cuam tshuam, TDM ntawm glycerol yog 2.788 Debye thiab 6.840 Debye rau 3PVA-(C10) 2Na Alg, thaum cov nqi TDM tau nce mus rau 17.990 Debye, 8.848 Debye, 5.874 Debye, 7.568 Debye thiab 12.779 Debye thaum 3PVA-(C10) 2Na Alg sib cuam tshuam nrog 1, 2, 3, 4 thiab 5 units ntawm glycerol, feem. Qhov siab dua tus nqi TDM, qhov siab dua nws cov tshuaj tiv thaiv nrog ib puag ncig.
Tag nrho lub zog (E) kuj tau suav, thiab cov nqi E ntawm glycerol thiab 3PVA-(C10)2 NaAlg tau pom tias yog -141.833 eV thiab -200092.503 eV, feem. Lub caij no, cov qauv sawv cev rau 3PVA-(C10)2 NaAlg cuam tshuam nrog 1, 2, 3, 4 thiab 5 glycerol units; E dhau los ua -996.837, -1108.440, -1238.740, -1372.075 thiab -1548.031 eV, feem. Kev nce cov ntsiab lus glycerol ua rau txo qis tag nrho lub zog thiab yog li ntawd ua rau muaj kev nce ntxiv hauv kev ua haujlwm. Raws li kev suav tag nrho lub zog, nws tau xaus lus tias tus qauv molecule, uas yog 3PVA-2Na Alg-5 Gly, muaj kev cuam tshuam ntau dua li lwm tus qauv molecules. Qhov xwm txheej no cuam tshuam nrog lawv cov qauv. 3PVA-(C10)2NaAlg tsuas muaj ob pawg -COONa xwb, thaum lwm cov qauv muaj ob pawg -COONa tab sis nqa ntau pawg OH, uas txhais tau tias lawv cov kev ua haujlwm rau ib puag ncig nce ntxiv.
Ntxiv rau, lub zog ionization (IE) ntawm txhua qhov qauv raug txiav txim siab hauv txoj kev tshawb fawb no. Lub zog ionization yog ib qho tseem ceeb rau kev ntsuas qhov reactivity ntawm tus qauv kawm. Lub zog uas xav tau los txav ib lub electron los ntawm ib qho ntawm ib lub molecule mus rau infinity hu ua lub zog ionization. Nws sawv cev rau qib ntawm ionization (piv txwv li reactivity) ntawm lub molecule. Lub zog ionization siab dua, qhov reactivity qis dua. Cov txiaj ntsig IE ntawm 3PVA-(C10)2NaAlg cuam tshuam nrog 1, 2, 3, 4 thiab 5 glycerol units yog -9.256, -9.393, -9.393, -9.248 thiab -9.323 eV, feem, thaum IEs ntawm glycerol thiab 3PVA-(C10)2NaAlg yog -5.157 thiab -9.341 eV, feem. Txij li thaum ntxiv glycerol ua rau tus nqi IP txo qis, qhov kev ua haujlwm ntawm cov tshuaj molecular nce ntxiv, uas ua rau kev siv tau ntawm PVA / NaAlg / glycerol qauv molecule hauv cov khoom siv electrochemical.
Tus piav qhia thib tsib hauv Rooj 3 yog Log P, uas yog logarithm ntawm cov coefficient faib thiab siv los piav qhia seb cov qauv uas tab tom kawm yog hydrophilic lossis hydrophobic. Tus nqi Log P tsis zoo qhia txog lub molecule hydrophilic, txhais tau tias nws yaj tau yooj yim hauv dej thiab yaj tsis zoo hauv cov organic solvents. Tus nqi zoo qhia txog cov txheej txheem rov qab.
Raws li cov txiaj ntsig tau txais, nws tuaj yeem xaus lus tias tag nrho cov qauv yog hydrophilic, txij li lawv cov nqi Log P ​​(3PVA-(C10)2Na Alg − 1Gly, 3PVA-(C10)2Na Alg − 2Gly, 3PVA-(C10)2Na Alg − 3Gly, 3PVA-(C10)2Na Alg − 4Gly thiab 3PVA-(C10)2Na Alg − 5Gly) yog -3.537, -5.261, -6.342, -7.423 thiab -8.504, feem, thaum tus nqi Log P ntawm glycerol tsuas yog -1.081 thiab 3PVA-(C10)2Na Alg tsuas yog -3.100. Qhov no txhais tau tias cov khoom ntawm cov qauv uas tau kawm yuav hloov pauv thaum cov dej molecules tau koom ua ke rau hauv nws cov qauv.
Thaum kawg, qhov polarizabilities ntawm txhua qhov qauv kuj raug suav ntawm qib PM6 siv txoj kev semi-empirical. Yav dhau los nws tau sau tseg tias qhov polarizabilities ntawm feem ntau cov ntaub ntawv nyob ntawm ntau yam. Qhov tseem ceeb tshaj plaws yog qhov ntim ntawm cov qauv uas tab tom kawm. Rau txhua qhov qauv uas cuam tshuam nrog thawj hom kev sib cuam tshuam ntawm 3PVA thiab 2NaAlg (kev sib cuam tshuam tshwm sim los ntawm carbon atom tus lej 10), qhov polarizabilities tau txhim kho los ntawm kev ntxiv glycerol. Qhov polarizabilities nce ntxiv los ntawm 29.690 Å mus rau 35.076, 40.665, 45.177, 50.239 thiab 54.638 Å vim muaj kev sib cuam tshuam nrog 1, 2, 3, 4 thiab 5 glycerol units. Yog li, nws tau pom tias tus qauv molecule nrog qhov siab tshaj plaws polarizability yog 3PVA-(C10)2NaAlg−5Gly, thaum tus qauv molecule nrog qhov qis tshaj plaws polarizability yog 3PVA-(C10)2NaAlg, uas yog 29.690 Å.
Kev ntsuam xyuas cov lus piav qhia QSAR tau qhia tias cov qauv uas sawv cev rau 3PVA-(C10)2NaAlg − 5Gly yog qhov ua rau muaj kev cuam tshuam thawj zaug.
Rau hom kev sib cuam tshuam thib ob ntawm PVA trimer thiab NaAlg dimer, cov txiaj ntsig qhia tau tias lawv cov nqi zoo ib yam li cov uas tau hais hauv ntu dhau los rau thawj qhov kev sib cuam tshuam. Txhua lub qauv muaj xoom tus nqi hluav taws xob, uas txhais tau tias lawv txhua tus nyob hauv lub xeev av.
Raws li tau pom hauv Rooj 4, cov nqi TDM (xam ntawm PM6 theem) ntawm Term 1 Na Alg − 3PVA-Mid 1 Na Alg tau nce ntxiv los ntawm 11.581 Debye mus rau 15.756, 19.720, 21.756, 22.732, 15.507, thiab 15.756 thaum Term 1 Na Alg − 3PVA-Mid 1 Na Alg tau cuam tshuam nrog 1, 2, 3, 4, 5, thiab 6 units ntawm glycerol. Txawm li cas los xij, tag nrho lub zog txo qis nrog rau qhov nce ntawm cov glycerol units, thiab thaum Lub Sijhawm 1 Na Alg − 3PVA- Mid 1 Na Alg cuam tshuam nrog qee tus lej ntawm glycerol units (1 txog 6), tag nrho lub zog yog − 996.985, − 1129.013, − 1267.211, − 1321.775, − 1418.964, thiab − 1637.432 eV, raws li.
Rau qhov thib ob qhov tshwm sim ntawm kev sib cuam tshuam, IP, Log P thiab polarizability kuj raug suav ntawm PM6 qib ntawm kev xav. Yog li ntawd, lawv tau xav txog peb qhov piav qhia muaj zog tshaj plaws ntawm kev ua haujlwm ntawm cov tshuaj molecular. Rau cov qauv uas sawv cev rau End 1 Na Alg-3PVA-Mid 1 Na Alg sib cuam tshuam nrog 1, 2, 3, 4, 5 thiab 6 glycerol units, IP nce ntxiv los ntawm −9.385 eV mus rau −8.946, −8.848, −8.430, −9.537, −7.997 thiab −8.900 eV. Txawm li cas los xij, tus nqi Log P uas tau xam tau qis dua vim yog kev ua kom zoo ntawm End 1 Na Alg-3PVA-Mid 1 Na Alg nrog glycerol. Raws li cov ntsiab lus glycerol nce ntxiv ntawm 1 mus rau 6, nws cov nqi dhau los ua -5.334, -6.415, -7.496, -9.096, -9.861 thiab -10.53 es tsis txhob -3.643. Thaum kawg, cov ntaub ntawv polarizability qhia tau hais tias kev nce cov ntsiab lus glycerol ua rau muaj kev nce ntawm polarizability ntawm Term 1 Na Alg- 3PVA- Mid 1 Na Alg. Lub polarizability ntawm tus qauv molecule Term 1 Na Alg- 3PVA- Mid 1 Na Alg nce ntxiv ntawm 31.703 Å mus rau 63.198 Å tom qab kev sib cuam tshuam nrog 6 glycerol units. Nws yog ib qho tseem ceeb uas yuav tsum nco ntsoov tias kev nce tus lej ntawm glycerol units hauv qhov kev sib cuam tshuam thib ob yog ua kom paub tseeb tias txawm tias muaj ntau tus atoms thiab cov qauv nyuaj, qhov kev ua tau zoo tseem zoo dua nrog kev nce ntawm cov ntsiab lus glycerol. Yog li, nws tuaj yeem hais tias tus qauv PVA / Na Alg / glycerin muaj peev xwm hloov cov roj teeb lithium-ion ib nrab, tab sis xav tau kev tshawb fawb thiab kev txhim kho ntxiv.
Kev piav qhia txog lub peev xwm khi ntawm ib qho chaw rau ib qho adsorbate thiab kev soj ntsuam qhov kev sib cuam tshuam tshwj xeeb ntawm cov kab ke yuav tsum paub txog hom kev sib txuas uas muaj nyob nruab nrab ntawm ob lub atoms, qhov nyuaj ntawm kev sib cuam tshuam intermolecular thiab intramolecular, thiab qhov faib ntawm electron density ntawm qhov chaw thiab adsorbent. Qhov electron density ntawm qhov chaw tseem ceeb ntawm kev sib txuas (BCP) ntawm cov atoms sib cuam tshuam yog qhov tseem ceeb rau kev soj ntsuam lub zog sib txuas hauv QTAIM kev tshuaj xyuas. Qhov siab dua ntawm qhov ceev ntawm electron, qhov ruaj khov dua ntawm kev sib cuam tshuam covalent thiab, feem ntau, qhov siab dua ntawm electron density ntawm cov ntsiab lus tseem ceeb no. Ntxiv mus, yog tias ob qho tib si tag nrho cov electron zog ceev (H (r)) thiab Laplace charge density (∇2ρ (r)) tsawg dua 0, qhov no qhia txog qhov muaj covalent (dav dav) kev sib cuam tshuam. Ntawm qhov tod tes, thaum ∇2ρ (r) thiab H (r) ntau dua 0.54, nws qhia txog qhov muaj cov kev sib cuam tshuam tsis-covalent (kaw plhaub) xws li cov hydrogen bonds tsis muaj zog, van der Waals forces thiab electrostatic kev sib cuam tshuam. Kev tshuaj xyuas QTAIM tau qhia txog qhov xwm txheej ntawm kev sib cuam tshuam tsis yog-covalent hauv cov qauv kawm raws li pom hauv Daim Duab 7 thiab 8. Raws li kev tshuaj xyuas, cov qauv molecules sawv cev rau 3PVA − 2Na Alg thiab Term 1 Na Alg − 3PVA –Mid 1 Na Alg tau qhia txog kev ruaj khov siab dua li cov molecules sib cuam tshuam nrog cov chav glycine sib txawv. Qhov no yog vim muaj ntau qhov kev sib cuam tshuam tsis yog-covalent uas muaj ntau dua hauv cov qauv alginate xws li kev sib cuam tshuam electrostatic thiab hydrogen bonds ua rau alginate ruaj khov cov composites. Ntxiv mus, peb cov txiaj ntsig qhia txog qhov tseem ceeb ntawm kev sib cuam tshuam tsis yog-covalent ntawm 3PVA − 2Na Alg thiab Term 1 Na Alg − 3PVA –Mid 1 Na Alg qauv molecules thiab glycine, qhia tias glycine ua lub luag haujlwm tseem ceeb hauv kev hloov kho qhov chaw ib puag ncig hluav taws xob ntawm cov composites.
Kev tshuaj xyuas QTAIM ntawm tus qauv molecule 3PVA − 2NaAlg cuam tshuam nrog (a) 0 Gly, (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, thiab (f) 5Gly.