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Ngenxa yobuninzi be-sodium resource, iibhetri ze-sodium-ion (ii-NIB) zimele isisombululo esithembisayo sokugcina amandla e-electrochemical. Okwangoku, umqobo ophambili kuphuhliso lwetekhnoloji ye-NIB kukungabikho kwezinto ze-electrode ezinokugcina/zikhuphe ii-sodium ion ixesha elide. Ke ngoko, injongo yolu phononongo kukuphanda ngokwethiyori isiphumo sokongeza i-glycerol kwi-polyvinyl alcohol (PVA) kunye ne-sodium alginate (NaAlg) blends njengezinto ze-NIB electrode. Olu phononongo lugxile kwiinkcazo ze-elektroniki, i-thermal, kunye ne-quantitative structure-activity relationship (QSAR) ze-polymer electrolytes ezisekelwe kwi-PVA, i-sodium alginate, kunye ne-glycerol blends. Ezi mpawu ziphandwa kusetyenziswa iindlela ze-semi-empirical kunye ne-density functional theory (DFT). Ekubeni uhlalutyo lwesakhiwo lutyhile iinkcukacha zonxibelelwano phakathi kwe-PVA/alginate kunye ne-glycerol, i-band gap energy (Eg) iphandwe. Iziphumo zibonisa ukuba ukongezwa kwe-glycerol kubangela ukwehla kwexabiso le-Eg ukuya kwi-0.2814 eV. Umphezulu we-molecular electrostatic potential (MESP) ubonisa ukusasazwa kweendawo ezityebileyo kwi-electron kunye ne-electron-poor kunye nee-molecule charges kwinkqubo yonke ye-electrolyte. Iiparameter zobushushu ezifundwe ziquka i-enthalpy (H), i-entropy (ΔS), umthamo wobushushu (Cp), amandla asimahla e-Gibbs (G) kunye nobushushu bokwakheka. Ukongeza, iinkcukacha ezininzi zobudlelwane besakhiwo-umsebenzi (QSAR) ezifana ne-total dipole moment (TDM), amandla apheleleyo (E), amandla e-ionization (IP), i-Log P kunye ne-polarizability ziphandwe kolu phononongo. Iziphumo zibonise ukuba i-H, i-ΔS, i-Cp, i-G kunye ne-TDM zanda ngokwanda kobushushu kunye nomxholo we-glycerol. Okwangoku, ubushushu bokwakheka, i-IP kunye ne-E buyehla, nto leyo eyaphucula i-reactivity kunye ne-polarizability. Ukongeza, ngokongeza i-glycerol, i-voltage yeseli yanda ukuya kwi-2.488 V. DFT kunye ne-PM6 calculations ngokusekelwe kwi-PVA/Na Alg glycerol-based electrolytes ezisebenzisa iindleko zibonisa ukuba zinokutshintsha iibhetri ze-lithium-ion ngenxa yokusebenza kwazo okuninzi, kodwa kufuneka uphuculo olongezelelweyo kunye nophando.
Nangona iibhetri ze-lithium-ion (LIBs) zisetyenziswa kakhulu, ukusetyenziswa kwazo kujongana nemida emininzi ngenxa yobomi bazo obufutshane, iindleko eziphezulu, kunye neenkxalabo zokhuseleko. Iibhetri ze-Sodium-ion (SIBs) zinokuba yindlela efanelekileyo yokutshintsha ii-LIBs ngenxa yokufumaneka kwazo ngokubanzi, iindleko eziphantsi, kunye nokungabi natyhefu kwento ye-sodium. Iibhetri ze-Sodium-ion (SIBs) ziya ziba yinkqubo yokugcina amandla ebalulekileyo kwizixhobo ze-electrochemical1. Iibhetri ze-Sodium-ion zixhomekeke kakhulu kwii-electrolytes ukwenza lula ukuthuthwa kwee-ion kunye nokuvelisa umbane wamandla2,3. Ii-electrolytes ezingamanzi zenziwe ikakhulu ziityuwa zesinyithi kunye nezinyibilikisi zendalo. Ukusetyenziswa okusebenzayo kufuna ukuqwalaselwa ngononophelo kokhuseleko lwee-electrolytes ezingamanzi, ingakumbi xa ibhetri iphantsi koxinzelelo lobushushu okanye lombane4.
Iibhetri zeSodium-ion (iiSIB) kulindeleke ukuba zithathe indawo yeebhetri zeLithium-ion kungekudala ngenxa yobuninzi bazo bokugcina ulwandle, ukungabi natyhefu, kunye nexabiso eliphantsi lezinto ezibonakalayo. Ukwenziwa kwezinto zeNanomaterials kukhawulezise uphuhliso lokugcina idatha, izixhobo ze-elektroniki, kunye ne-optical. Uluhlu olukhulu lweencwadi lubonise ukusetyenziswa kwezakhiwo ezahlukeneyo zeNano (umz., iiMetal oxides, iGraphene, iiNanotubes, kunye neeFullerenes) kwiibhetri zeSodium-ion. Uphando lugxile kuphuhliso lwezinto ze-anode, kubandakanya iiPolymer, kwiibhetri zeSodium-ion ngenxa yokuguquguquka kwazo kunye nobuhlobo nokusingqongileyo. Umdla wophando kwicandelo leebhetri zePolymer ezinokutshajwa kwakhona ngokuqinisekileyo uya kwanda. Izixhobo ezintsha zePolymer electrode ezinezakhiwo kunye neempawu ezizodwa zinokuvula indlela yetekhnoloji yokugcina amandla enobuhlobo nokusingqongileyo. Nangona izixhobo ezahlukeneyo zePolymer electrode ziye zahlolwa ukuze zisetyenziswe kwiibhetri zeSodium-ion, eli candelo lisekwinqanaba lokuqala lophuhliso. Kwiibhetri zeSodium-ion, izixhobo zePolymer ezininzi ezineemo ezahlukeneyo zesakhiwo kufuneka zihlolwe. Ngokusekelwe kulwazi lwethu lwangoku malunga nendlela yokugcina ii-ion ze-sodium kwizixhobo ze-polymer electrode, kunokucingelwa ukuba amaqela e-carbonyl, ii-free radicals, kunye nee-heteroatom kwinkqubo edibeneyo zinokusebenza njengeendawo ezisebenzayo zokusebenzisana nee-ion ze-sodium. Ke ngoko, kubalulekile ukuphuhlisa ii-polymers ezintsha ezinoxinano olukhulu lwezi ndawo zisebenzayo. I-gel polymer electrolyte (GPE) yitekhnoloji eyahlukileyo ephucula ukuthembeka kwebhetri, ukuqhuba kwee-ion, ukungavuzi, ukuguquguquka okuphezulu, kunye nokusebenza kakuhle12.
Iimatrices zePolymer ziquka izinto ezifana ne-PVA kunye ne-polyethylene oxide (PEO)13. I-gel permeable polymer (GPE) ithintela i-electrolyte engamanzi kwi-polymer matrix, nto leyo enciphisa umngcipheko wokuvuza xa kuthelekiswa nabahlukanisi bezorhwebo14. I-PVA yi-polymer ebolileyo eyenziweyo. Ine-permittivity ephezulu, ayibizi kwaye ayinatyhefu. Le nto yaziwa ngeempawu zayo zokwenza ifilimu, uzinzo lweekhemikhali kunye nokunamathela. Ikwanamaqela asebenzayo (OH) kunye noxinano oluphezulu lwe-cross-linking potential15,16,17. Ukuxuba i-polymer, ukongeza i-plasticizer, ukongeza i-composite kunye neendlela ze-polymerization ze-in situ zisetyenzisiwe ukuphucula ukuqhuba kwe-polymers ze-polymer ezisekwe kwi-PVA ukunciphisa i-crystallinity ye-matrix kunye nokwandisa ukuguquguquka kwe-chain18,19,20.
Ukuxuba yindlela ebalulekileyo yokuphuhlisa izixhobo zepolymeric kwizicelo zoshishino. Iingxube zepolymer zihlala zisetyenziselwa: (1) ukuphucula iipropati zokucubungula iipolymers zendalo kwizicelo zoshishino; (2) ukuphucula iipropati zeekhemikhali, zomzimba, kunye nezoomatshini zezinto ezinokubola; kunye (3) ukuziqhelanisa nesidingo esitshintsha ngokukhawuleza sezixhobo ezintsha kwishishini lokupakisha ukutya. Ngokungafaniyo ne-copolymerization, ukuxuba ipolymer yinkqubo engabizi kakhulu esebenzisa iinkqubo ezilula zomzimba kuneenkqubo zeekhemikhali ezintsonkothileyo ukufezekisa iipropati ezifunwayo21. Ukwenza ii-homopolymers, iipolymers ezahlukeneyo zinokusebenzisana ngamandla e-dipole-dipole, iibhondi ze-hydrogen, okanye ii-complexes zokudlulisa itshaja22,23. Iingxube ezenziwe ngeepolymers zendalo kunye nezokwenziwa zinokudibanisa ukuhambelana okuhle kwezinto eziphilayo kunye neepropati ezintle zoomatshini, zenze izinto eziphezulu ngexabiso eliphantsi lemveliso24,25. Ke ngoko, kubekho umdla omkhulu ekudaleni izinto zepolymeric ezihambelana ne-bio ngokudibanisa iipolymers zokwenziwa kunye nezendalo. I-PVA inokudityaniswa ne-sodium alginate (NaAlg), i-cellulose, i-chitosan kunye ne-starch26.
I-Sodium alginate yi-polymer yendalo kunye ne-anionic polysaccharide ethathwe kwi-algae emdaka yolwandle. I-Sodium alginate ine-β-(1-4)-linked D-mannuronic acid (M) kunye ne-α-(1-4)-linked L-guluronic acid (G) ehlelwe kwiifom ze-homopolymeric (poly-M kunye ne-poly-G) kunye neebhloko ze-heteropolymeric (MG okanye GM)27. Umlinganiselo womxholo kunye nomlinganiselo ohambelanayo weebhloko ze-M kunye ne-G unefuthe elikhulu kwiimpawu zekhemikhali kunye nezomzimba ze-alginate28,29. I-Sodium alginate isetyenziswa kakhulu kwaye ifundwa ngenxa yokubola kwayo, ukuhambelana kwayo nezinto eziphilayo, iindleko eziphantsi, iimpawu ezilungileyo zokwenza ifilimu, kunye nokungabi natyhefu. Nangona kunjalo, inani elikhulu lamaqela e-free hydroxyl (OH) kunye ne-carboxylate (COO) kwi-alginate chain yenza i-alginate ibe ne-hydrophilic kakhulu. Nangona kunjalo, i-alginate ineempawu ezimbi zoomatshini ngenxa yokuba buthathaka kunye nokuqina kwayo. Ngoko ke, i-alginate ingadityaniswa nezinye izinto ezenziweyo ukuphucula uvakalelo lwamanzi kunye neempawu zoomatshini30,31.
Ngaphambi kokuba kuyile izinto ezintsha ze-electrode, izibalo ze-DFT zihlala zisetyenziselwa ukuvavanya ukuba kunokwenzeka na ukwenziwa kwezinto ezintsha. Ukongeza, izazinzulu zisebenzisa i-molecular modeling ukuqinisekisa nokuqikelela iziphumo zovavanyo, ukonga ixesha, ukunciphisa inkunkuma yamakhemikhali, kunye nokuqikelela ukuziphatha kokunxibelelana32. I-molecular modeling ibe lisebe elinamandla nelibalulekileyo lesayensi kwiinkalo ezininzi, kubandakanya isayensi yezinto, izinto ze-nanomaterials, i-computational chemistry, kunye nokufunyanwa kweziyobisi33,34. Besebenzisa iinkqubo ze-modeling, izazinzulu zinokufumana idatha ye-molecular ngokuthe ngqo, kubandakanya amandla (ubushushu bokwakheka, amandla e-ionization, amandla okusebenza, njl.njl.) kunye ne-geometry (ii-bond angles, ubude be-bond, kunye nee-torsion angles)35. Ukongeza, iipropati ze-elektroniki (itshaja, amandla e-HOMO kunye ne-LUMO band gap, i-electron affinity), iipropati ze-spectral (iindlela zokudlidliza kunye namandla afana ne-FTIR spectra), kunye neepropati ze-bulk (umthamo, ukusasazwa, i-viscosity, i-modulus, njl.njl.)36 zinokubalwa.
I-LiNiPO4 ibonisa iingenelo ezinokubakho zokukhuphisana nezixhobo ze-electrode ze-lithium-ion ngenxa yoxinano lwayo lwamandla aphezulu (i-voltage yokusebenza emalunga ne-5.1 V). Ukuze basebenzise ngokupheleleyo inzuzo ye-LiNiPO4 kummandla we-voltage ephezulu, i-voltage yokusebenza kufuneka yehliswe kuba i-electrolyte ephezulu ephuhlisiwe ngoku inokuhlala izinzile kuphela kwii-voltage ezingaphantsi kwe-4.8 V. UZhang et al. baphande nge-doping yazo zonke ii-transition metals ze-3d, 4d, kunye ne-5d kwindawo ye-Ni ye-LiNiPO4, bakhetha iipateni ze-doping ezine-electrochemical performance entle kakhulu, kwaye balungisa i-voltage yokusebenza ye-LiNiPO4 ngelixa begcina uzinzo oluhambelanayo lwe-electrochemical performance yayo. Ii-voltage zokusebenza eziphantsi abazifumeneyo yayiyi-4.21, 3.76, kunye ne-3.5037 kwi-Ti, Nb, kunye ne-Ta-doped LiNiPO4, ngokwahlukeneyo.
Ngoko ke, injongo yolu phononongo kukuphanda ngokwethiyori impembelelo ye-glycerol njenge-plasticizer kwiipropati ze-elektroniki, iinkcazo ze-QSAR kunye neepropati zobushushu zenkqubo ye-PVA/NaAlg kusetyenziswa izibalo ze-quantum mechanical zokusetyenziswa kwayo kwiibhetri ze-ion-ion ezinokutshajwa kwakhona. Ukusebenzisana kweemolekyuli phakathi kwemodeli ye-PVA/NaAlg kunye ne-glycerol kuhlalutywe kusetyenziswa ithiyori ye-atomic ye-quantum kaBader (QTAIM).
Imodeli yemolekyuli emele ukusebenzisana kwe-PVA ne-NaAlg kunye ne-glycerol yenziwe ngcono kusetyenziswa i-DFT. Imodeli ibalwe kusetyenziswa isoftware ye-Gaussian 0938 kwiSebe leSpectroscopy, iZiko loPhando leSizwe, eCairo, e-Egypt. Iimodeli zenziwe ngcono kusetyenziswa i-DFT kwinqanaba le-B3LYP/6-311G(d, p)39,40,41,42. Ukuqinisekisa ukusebenzisana phakathi kweemodeli ezifundweyo, izifundo ze-frequency ezenziwe kwinqanaba elifanayo lethiyori zibonisa uzinzo lwe-geometry ephuculweyo. Ukungabikho kwe-negative frequency phakathi kwazo zonke ii-frequency ezivavanyiweyo kugxininisa isakhiwo esiqikelelweyo kwi-minima ye-positive yokwenyani kumphezulu wamandla anokubakho. Iiparameter zomzimba ezifana ne-TDM, amandla e-HOMO/LUMO band gap kunye ne-MESP zibalwe kwinqanaba elifanayo lethiyori ye-quantum mechanical. Ukongeza, ezinye iiparameter zobushushu ezifana nobushushu bokugqibela bokwakheka, amandla akhululekileyo, i-entropy, i-enthalpy kunye nomthamo wobushushu zibalwe kusetyenziswa iifomyula ezinikiweyo kwiTheyibhile 1. Iimodeli ezifundiweyo ziphantsi kohlalutyo lwe-quantum theory yee-athomu kwiimolekyuli (i-QTAIM) ukuze kuchongwe ukusebenzisana okwenzeka kumphezulu wezakhiwo ezifundiweyo. Ezi zibalo zenziwe kusetyenziswa umyalelo othi “output=wfn” kwikhowudi yesoftware yeGaussian 09 kwaye emva koko zabonwa kusetyenziswa ikhowudi yesoftware ye-Avogadro43.
Apho u-E ngamandla angaphakathi, u-P luxinzelelo, u-V ngumthamo, u-Q lutshintshiselwano lobushushu phakathi kwenkqubo kunye nendawo engqongileyo, u-T bubushushu, u-ΔH lutshintsho lwe-enthalpy, u-ΔG lutshintsho lwamandla asimahla, u-ΔS lutshintsho lwe-entropy, u-a kunye no-b ziiparameter zokungcangcazela, u-q ngumrhumo we-athomu, kwaye u-C nguxinano lwe-electron ye-athomu44,45. Okokugqibela, izakhiwo ezifanayo zenziwe ngcono kwaye iiparameter ze-QSAR zabalwa kwinqanaba le-PM6 kusetyenziswa ikhowudi yesoftware ye-SCIGRESS46 kwiSebe leSpectroscopy leZiko loPhando leSizwe eCairo, eYiputa.
Kumsebenzi wethu wangaphambili47, sivavanye imodeli enokwenzeka kakhulu echaza ukusebenzisana kweeyunithi ezintathu ze-PVA kunye neeyunithi ezimbini ze-NaAlg, apho i-glycerol isebenza njenge-plasticizer. Njengoko kukhankanyiwe ngasentla, kukho amathuba amabini okusebenzisana kwe-PVA kunye ne-NaAlg. Ezi modeli zimbini, ezibizwa ngokuba yi-3PVA-2Na Alg (ngokusekwe kwinombolo yekhabhoni 10) kunye neTerm 1Na Alg-3PVA-Mid 1Na Alg, zinexabiso elincinci kakhulu le-energy gap48 xa kuthelekiswa nezinye izakhiwo eziqwalaselweyo. Ke ngoko, isiphumo sokongeza kwe-Gly kwimodeli enokwenzeka kakhulu ye-PVA/Na Alg blend polymer siphandwe kusetyenziswa izakhiwo ezimbini zokugqibela: i-3PVA-(C10)2Na Alg (ebizwa ngokuba yi-3PVA-2Na Alg ngokulula) kunye neTerm 1 Na Alg − 3PVA-Mid 1 Na Alg. Ngokweencwadi, i-PVA, i-NaAlg kunye ne-glycerol zinokwenza kuphela iibhondi ze-hydrogen ezibuthathaka phakathi kwamaqela asebenzayo e-hydroxyl. Ekubeni zombini i-PVA trimer kunye ne-NaAlg kunye ne-glycerol dimer ziqulathe amaqela amaninzi e-OH, unxibelelwano lunokufunyanwa ngelinye lamaqela e-OH. Umfanekiso 1 ubonisa ukusebenzisana phakathi kwe-molecule ye-glycerol yemodeli kunye ne-molecule yemodeli 3PVA-2Na Alg, kwaye Umfanekiso 2 ubonisa imodeli eyakhiweyo yokusebenzisana phakathi kwe-molecule yemodeli Ithemu 1Na Alg-3PVA-Mid 1Na Alg kunye noxinzelelo olwahlukeneyo lwe-glycerol.
Izakhiwo ezilungiselelweyo: (a) I-Gly kunye ne-3PVA − 2Na Alg zidibana ne (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, kunye (f) 5 Gly.
Izakhiwo ezilungiselelweyo zeTerm 1Na Alg- 3PVA –Mid 1Na Alg ezisebenzisana ne (a) 1 Gly, (b) 2 Gly, (c) 3 Gly, (d) 4 Gly, (e) 5 Gly, kunye (f) 6 Gly.
Amandla e-electron band gap yiparameter ebalulekileyo ekufuneka iqwalaselwe xa kufundwa ukwenzeka kwayo nayiphi na into ye-electrode. Kuba ichaza indlela ezisebenza ngayo ii-electron xa izinto zitshintsha ngaphandle. Ke ngoko, kuyimfuneko ukuqikelela amandla e-electron band gap e-HOMO/LUMO kuzo zonke izakhiwo ezifundwe. Itheyibhile 2 ibonisa utshintsho kumandla e-HOMO/LUMO e-3PVA-(C10)2Na Alg kunye neTerm 1Na Alg − 3PVA-Mid 1Na Alg ngenxa yokongezwa kwe-glycerol. Ngokwe-ref47, ixabiso le-Eg le-3PVA-(C10)2Na Alg yi-0.2908 eV, ngelixa ixabiso le-Eg lesakhiwo libonisa amathuba okusebenzisana kwesibini (oko kukuthi, iTerm 1Na Alg − 3PVA-Mid 1Na Alg) yi-0.5706 eV.
Nangona kunjalo, kufunyenwe ukuba ukongezwa kwe-glycerol kubangele utshintsho oluncinci kwixabiso le-Eg le-3PVA-(C10)2Na Alg. Xa i-3PVA-(C10)2NaAlg isebenzisana neeyunithi ze-glycerol eziyi-1, 2, 3, 4 kunye ne-5, amaxabiso ayo e-Eg aba yi-0.302, 0.299, 0.308, 0.289 kunye ne-0.281 eV, ngokwahlukeneyo. Nangona kunjalo, kukho ukuqonda okubalulekileyo kokuba emva kokongeza iiyunithi ze-glycerol ezi-3, ixabiso le-Eg laba lincinci kunele-3PVA-(C10)2Na Alg. Imodeli emele ukusebenzisana kwe-3PVA-(C10)2Na Alg kunye neeyunithi ze-glycerol ezintlanu yeyona modeli inokwenzeka yokusebenzisana. Oku kuthetha ukuba njengoko inani leeyunithi ze-glycerol lisanda, amathuba okusebenzisana nawo ayanda.
Okwangoku, kwithuba lesibini lokusebenzisana, amandla e-HOMO/LUMO ee-molecule zemodeli ezimele iTerm 1Na Alg − 3PVA –Mid 1Na Alg- 1Gly, Term 1Na Alg − 3PVA –Mid 1Na Alg- 2Gly, Term 1Na Alg − 3PVA –Mid 1Na Alg- 3Gly, Term 1Na Alg − 3PVA –Mid 1Na Alg- 4Gly, Term 1Na Alg − 3PVA –Mid 1Na Alg- 5Gly kunye neTerm 1Na Alg − 3PVA –Mid 1Na Alg- 6Gly ziba yi-1.343, 1.34 7, 0.976, 0.607, 0.348 kunye ne-0.496 eV, ngokulandelelana. Itheyibhile 2 ibonisa amandla e-HOMO/LUMO band gap abaliweyo kuzo zonke izakhiwo. Ngaphezu koko, indlela efanayo yokuziphatha kwamathuba okunxibelelana kweqela lokuqala iphindaphindwa apha.
Ithiyori yebhendi kwifiziksi yesimo esiqinileyo ithi njengoko umsantsa webhendi wezinto ze-electrode uncipha, ukuhanjiswa kwe-elektroniki kwezinto kuyanda. Ukutsalwa kwedophi yindlela eqhelekileyo yokunciphisa umsantsa webhendi wezinto ze-cathode ze-sodium-ion. UJiang nabanye basebenzise i-Cu doping ukuphucula ukuhanjiswa kwe-elektroniki kwezinto ezifakwe kwi-β-NaMnO2. Besebenzisa izibalo ze-DFT, bafumanise ukuba ukutsalwa kwedophi kunciphisa umsantsa webhendi wezinto ukusuka kwi-0.7 eV ukuya kwi-0.3 eV. Oku kubonisa ukuba ukutsalwa kwe-Cu kuphucula ukuhanjiswa kwe-elektroniki kwezinto ze-β-NaMnO2.
I-MESP ichazwa njengamandla okusebenzisana phakathi kokusasazwa kwe-molecular charge kunye ne-single positive charge. I-MESP ithathwa njengesixhobo esisebenzayo sokuqonda nokutolika iipropati zeekhemikhali kunye nokusebenza kwakhona. I-MESP ingasetyenziselwa ukuqonda iindlela zokusebenzisana phakathi kwezinto ze-polymeric. I-MESP ichaza ukusasazwa kwe-charge ngaphakathi kwekhompawundi efundwayo. Ukongeza, i-MESP inika ulwazi malunga neendawo ezisebenzayo kwizixhobo ezifundwayo32. Umfanekiso 3 ubonisa iiploti ze-MESP ze-3PVA-(C10) 2Na Alg, 3PVA-(C10) 2Na Alg − 1Gly, 3PVA-(C10) 2Na Alg − 2Gly, 3PVA-(C10) 2Na Alg − 3Gly, 3PVA-(C10) 2Na Alg − 4Gly, kunye ne-3PVA-(C10) 2Na Alg − 5Gly eqikelelwe kwinqanaba le-B3LYP/6-311G(d, p) yethiyori.
Iikhontuthi ze-MESP zibalwe nge-B3LYP/6-311 g(d, p) ze-(a) Gly kunye ne-3PVA − 2Na Alg ezisebenzisana ne-(b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, kunye ne-(f) 5 Gly.
Okwangoku, uMfanekiso 4 ubonisa iziphumo ezibaliweyo ze-MESP kwikota 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 − 3gly, Term 1Na Alg-3PVA – Mid 1Na Alg − 4Gly, Term 1Na Alg-3PVA – Mid 1Na Alg-5gly kunye Term 1Na Alg-3PVA – Mid 1Na Alg − 6Gly, ngokulandelelana. I-MESP ebaliweyo imelwe njengendlela yokuziphatha kwe-contour. Imigca ye-contour imelwe yimibala eyahlukeneyo. Umbala ngamnye umele ixabiso elahlukileyo le-electronegativity. Umbala obomvu ubonisa iindawo ezine-electronegative okanye ezisabela kakhulu. Okwangoku, umbala otyheli umele iindawo ezingathathi cala 49, 50, 51 kwisakhiwo. Iziphumo ze-MESP zibonise ukuba i-reactivity ye-3PVA-(C10)2Na Alg inyukile ngokwanda kombala obomvu ojikeleze iimodeli ezifundiweyo. Okwangoku, ubukhali bombala obomvu kwimephu ye-MESP ye-Term 1Na Alg-3PVA – Mid 1Na Alg model molecule buyancipha ngenxa yokusebenzisana nomxholo owahlukileyo we-glycerol. Utshintsho kulwabiwo lombala obomvu ojikeleze isakhiwo esicetywayo lubonisa i-reactivity, ngelixa ukwanda kobukhali kuqinisekisa ukwanda kwe-electronegativity ye-3PVA-(C10)2Na Alg model molecule ngenxa yokwanda komxholo we-glycerol.
I-B3LYP/6-311 g(d, p) ibalwe i-MESP Ixesha le-1Na Alg-3PVA-Mid 1Na Alg esebenzisana ne-(a) 1 Gly, (b) 2 Gly, (c) 3 Gly, (d) 4 Gly, (e) 5 Gly, kunye (f) 6 Gly.
Zonke izakhiwo ezicetywayo zinemilinganiselo yazo yobushushu efana ne-enthalpy, i-entropy, amandla obushushu, amandla asimahla kunye nobushushu bokwakheka obalwe kumaqondo obushushu ahlukeneyo ukusuka kwi-200 K ukuya kwi-500 K. Ukuchaza indlela eziziphatha ngayo iinkqubo zendalo, ukongeza ekufundeni indlela eziziphatha ngayo ze-elektroniki, kuyimfuneko nokufunda indlela eziziphatha ngayo zobushushu njengomsebenzi wobushushu ngenxa yokusebenzisana kwazo, nto leyo enokubalwa kusetyenziswa ii-equations ezinikwe kwiTheyibhile 1. Uphononongo lwezi parameters zobushushu luthathwa njengophawu olubalulekileyo lokuphendula kunye nokuzinza kweenkqubo zendalo ezinjalo kumaqondo obushushu ahlukeneyo.
Ngokuphathelele i-enthalpy ye-PVA trimer, iqala isabela kwi-NaAlg dimer, ize idlule kwiqela le-OH eliqhotyoshelwe kwi-carbon atom #10, ize ekugqibeleni ibe ne-glycerol. I-Enthalpy sisilinganiselo samandla kwinkqubo ye-thermodynamic. I-Enthalpy ilingana nobushushu obupheleleyo kwinkqubo, obulingana namandla angaphakathi kwenkqubo kunye nemveliso yomthamo wayo kunye noxinzelelo. Ngamanye amazwi, i-enthalpy ibonisa ukuba bungakanani ubushushu kunye nomsebenzi obongezwayo okanye osuswayo kwinto ethile52.
Umfanekiso 5 ubonisa utshintsho lwe-enthalpy ngexesha lokusabela kwe-3PVA-(C10)2Na Alg enezinga ezahlukeneyo ze-glycerol. Izifinyezo A0, A1, A2, A3, A4, kunye ne-A5 zimele iimolekyuli zemodeli 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, kunye ne-3PVA-(C10)2Na Alg − 5Gly, ngokwahlukeneyo. Umfanekiso 5a ubonisa ukuba i-enthalpy iyanda ngobushushu obukhulayo kunye nomxholo we-glycerol. I-enthalpy yesakhiwo emele i-3PVA-(C10)2NaAlg − 5Gly (oko kukuthi, i-A5) kwi-200 K yi-27.966 cal/mol, ngelixa i-enthalpy yesakhiwo emele i-3PVA-2NaAlg kwi-200 K yi-13.490 cal/mol. Okokugqibela, ekubeni i-enthalpy ilungile, le mpendulo yi-endothermic.
I-Entropy ichazwa njengomlinganiselo wamandla angafumanekiyo kwinkqubo ye-thermodynamic evaliweyo kwaye idla ngokuthathwa njengomlinganiselo wokuphazamiseka kwenkqubo. Umfanekiso 5b ubonisa utshintsho kwi-entropy ye-3PVA-(C10)2NaAlg kunye nobushushu kunye nendlela esebenzisana ngayo neeyunithi ezahlukeneyo ze-glycerol. Igrafu ibonisa ukuba i-entropy iyatshintsha ngokulandelelana njengoko ubushushu bunyuka ukusuka kwi-200 K ukuya kwi-500 K. Umfanekiso 5b ubonisa ngokucacileyo ukuba i-entropy yemodeli ye-3PVA-(C10)2Na Alg ithambekele kwi-200 cal/K/mol kwi-200 K kuba imodeli ye-3PVA-(C10)2Na Alg ibonisa ukuphazamiseka okuncinci kwe-lattice. Njengoko ubushushu busanda, imodeli ye-3PVA-(C10)2Na Alg iyaphazamiseka kwaye ichaza ukunyuka kwe-entropy kunye nobushushu obukhulayo. Ngaphezu koko, kuyacaca ukuba ulwakhiwo lwe-3PVA-C10 2Na Alg-5 Gly lunexabiso eliphezulu le-entropy.
Ukuziphatha okufanayo kubonwa kuMfanekiso 5c, obonisa utshintsho kumthamo wobushushu kunye nobushushu. Umthamo wobushushu bubungakanani bobushushu obufunekayo ukutshintsha ubushushu bento ethile nge-1 °C47. Umfanekiso 5c ubonisa utshintsho kumthamo wobushushu wemolekyuli yemodeli i-3PVA-(C10)2NaAlg ngenxa yokusebenzisana neeyunithi ze-glycerol eziyi-1, 2, 3, 4, kunye ne-5. Umfanekiso ubonisa ukuba umthamo wobushushu wemodeli i-3PVA-(C10)2NaAlg uyanda ngokuthe ngqo kunye nobushushu. Ukwanda okubonakalayo kumthamo wobushushu kunye nobushushu obukhulayo kubangelwa kukungcangcazela kobushushu be-phonon. Ukongeza, kukho ubungqina bokuba ukwandisa umxholo we-glycerol kukhokelela ekwandeni komthamo wobushushu wemodeli i-3PVA-(C10)2NaAlg. Ngaphezu koko, isakhiwo sibonisa ukuba i-3PVA-(C10)2NaAlg−5Gly inexabiso eliphezulu lomthamo wobushushu xa kuthelekiswa nezinye izakhiwo.
Ezinye iiparameter ezifana namandla akhululekileyo kunye nobushushu bokugqibela bokwakheka zibalwe kwizakhiwo ezifundwayo kwaye ziboniswe kuMfanekiso 5d kunye no-e, ngokwahlukeneyo. Ubushushu bokugqibela bokwakheka bubushushu obukhutshwayo okanye obufunxwayo ngexesha lokwenziwa kwento ecocekileyo evela kwizinto zayo eziphantsi koxinzelelo oluqhubekayo. Amandla akhululekileyo anokuchazwa njengepropathi efana namandla, oko kukuthi, ixabiso lawo lixhomekeke kubungakanani bento kwimeko nganye ye-thermodynamic. Amandla akhululekileyo kunye nobushushu bokwakheka kwe-3PVA-(C10)2NaAlg−5Gly yayizezona ziphantsi kwaye zaziyi--1318.338 kunye ne--1628.154 kcal/mol, ngokwahlukeneyo. Ngokwahlukileyo koko, isakhiwo esimele i-3PVA-(C10)2NaAlg sinamandla akhululekileyo aphezulu kunye namaxabiso okwakheka kwe--690.340 kunye ne--830.673 kcal/mol, ngokwahlukeneyo, xa kuthelekiswa nezinye izakhiwo. Njengoko kubonisiwe kuMfanekiso 5, iipropati ezahlukeneyo zobushushu ziyatshintshwa ngenxa yokusebenzisana ne-glycerol. Amandla akhululekileyo e-Gibbs aphantsi, okubonisa ukuba isakhiwo esicetywayo sizinzile.
I-PM6 ibale iiparameter zobushushu ze-3PVA- (C10) 2Na Alg (imodeli A0), 3PVA- (C10) 2Na Alg − 1 Gly (imodeli A1), 3PVA- (C10) 2Na Alg − 2 Gly (imodeli A2), 3PVA- (C10) 2Na Alg − 3 Gly (imodeli A3), 3PVA- (C10) 2Na Alg − 4 Gly (imodeli A4), kunye ne-3PVA- (C10) 2Na Alg − 5 Gly (imodeli A5), apho (a) yi-enthalpy, (b) i-entropy, (c) amandla obushushu, (d) amandla asimahla, kunye (e) nobushushu bokwakheka.
Kwelinye icala, indlela yesibini yokusebenzisana phakathi kwe-PVA trimer kunye ne-dimeric NaAlg yenzeka kumaqela e-terminal kunye namaqela aphakathi e-OH kwisakhiwo se-PVA trimer. Njengakwiqela lokuqala, iiparameter zobushushu zibalwe kusetyenziswa inqanaba elifanayo lethiyori. Umfanekiso 6a-e ubonisa umahluko we-enthalpy, i-entropy, umthamo wobushushu, amandla asimahla, kwaye ekugqibeleni, ubushushu bokwakheka. Imifanekiso 6a-c ibonisa ukuba i-enthalpy, i-entropy kunye nomthamo wobushushu weTerm 1 NaAlg-3PVA-Mid 1 NaAlg zibonisa ukuziphatha okufanayo neqela lokuqala xa zisebenzisana neeyunithi ze-glycerol eziyi-1, 2, 3, 4, 5 kunye ne-6. Ngaphezu koko, amaxabiso azo ayanda kancinci kancinci ngobushushu obukhulayo. Ukongeza, kwimodeli ecetywayo yeTerm 1 Na Alg − 3PVA-Mid 1 Na Alg, amaxabiso e-enthalpy, entropy kunye nomthamo wobushushu anyuke ngokwanda komxholo we-glycerol. Izifinyezo B0, B1, B2, B3, B4, B5 kunye ne-B6 zimele ezi zakhiwo zilandelayo ngokulandelelana: Ikota 1 Na Alg − 3PVA- Mid 1 Na Alg, Ikota 1 Na Alg- 3PVA- Mid 1 Na Alg − 1 Gly, Ikota 1 Na Alg- 3PVA- Mid 1 Na Alg − 2gly, Ikota 1 Na Alg- 3PVA- Mid 1 Na Alg − 3gly, Ikota 1 Na Alg- 3PVA- Mid 1 Na Alg − 4 Gly, Ikota 1 Na Alg- 3PVA- Mid 1 Na Alg − 5 Gly kunye nekota 1 Na Alg- 3PVA- Mid 1 Na Alg − 6 Gly. Njengoko kubonisiwe kwiFig. 6a–c, kuyacaca ukuba amaxabiso e-enthalpy, entropy kunye nomthamo wobushushu ayanda njengoko inani leeyunithi ze-glycerol lisanda ukusuka kwi-1 ukuya kwi-6.
I-PM6 ibale iiparameter zobushushu zeTerm 1 Na Alg-3PVA- Mid 1 Na Alg (imodeli B0), Term 1 Na Alg-3PVA- Mid 1 Na Alg – 1 Gly (imodeli B1), Term 1 Na Alg-3PVA- Mid 1 Na Alg – 2 Gly (imodeli B2), Term 1 Na Alg-3PVA- Mid 1 Na Alg – 3 Gly (imodeli B3), Term 1 Na Alg-3PVA- Mid 1 Na Alg – 4 Gly (imodeli B4), Term 1 Na Alg-3PVA- Mid 1 Na Alg – 5 Gly (imodeli B5), kunye Term 1 Na Alg-3PVA- Mid 1 Na Alg – 6 Gly (imodeli B6), kuquka (a) i-enthalpy, (b) i-entropy, (c) amandla obushushu, (d) amandla asimahla, kunye (e) nobushushu bokwakheka.
Ukongeza, isakhiwo esimele iTerm 1 Na Alg-3PVA- Mid 1 Na Alg-6 Gly sinexabiso eliphezulu le-enthalpy, entropy kunye namandla obushushu xa kuthelekiswa nezinye izakhiwo. Phakathi kwazo, ixabiso lazo linyuke ukusuka kwi-16.703 cal/mol, 257.990 cal/mol/K kunye ne-131.323 kcal/mol kwiTerm 1 Na Alg − 3PVA- Mid 1 Na Alg ukuya kwi-33.223 cal/mol, 420.038 cal/mol/K kunye ne-275.923 kcal/mol kwiTerm 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly, ngokulandelelana.
Nangona kunjalo, iMifanekiso 6d kunye no-e zibonisa ukuxhomekeka kobushushu bamandla akhululekileyo kunye nobushushu bokugqibela bokwakheka (HF). I-HF ingachazwa njengotshintsho lwe-enthalpy olwenzeka xa i-mole enye yento yenziwe kwizinto zayo phantsi kweemeko zendalo neziqhelekileyo. Kuyabonakala kwimifanekiso ukuba amandla akhululekileyo kunye nobushushu bokugqibela bokwakheka kwazo zonke izakhiwo ezifundwayo zibonisa ukuxhomekeka okuthe ngqo kubushushu, oko kukuthi, zikhula kancinci kancinci nangomgca ngokwanda kobushushu. Ukongeza, lo mfanekiso ukwaqinisekisile ukuba isakhiwo esimele iTerm 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly sinamandla akhululekileyo asezantsi kunye neHF ephantsi. Zombini iiparameter zehle ukusuka kwi -758.337 ukuya kwi -899.741 K cal/mol kwikota 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly ukuya kwi -1,476.591 kunye ne -1,828.523 K cal/mol. Kuyabonakala kwiziphumo ukuba i-HF iyancipha ngokwanda kweeyunithi ze-glycerol. Oku kuthetha ukuba ngenxa yokwanda kwamaqela asebenzayo, i-reactivity nayo iyanda kwaye ngenxa yoko kufuneka amandla amancinci ukwenza i-reaction. Oku kuqinisekisa ukuba i-PVA/NaAlg eyenziwe ngeplastiki ingasetyenziswa kwiibhetri ngenxa ye-reactivity yayo ephezulu.
Ngokubanzi, iziphumo zobushushu zahlulwe zibe ziintlobo ezimbini: iziphumo zobushushu obuphantsi kunye neziphumo zobushushu obuphezulu. Iziphumo zobushushu obuphantsi zivakala kakhulu kumazwe akwiindawo eziphakamileyo, njengeGreenland, Canada, neRussia. Ebusika, ubushushu bomoya wangaphandle kwezi ndawo bungaphantsi kakhulu kwiidigri zeCelsius ezi-0. Ubomi kunye nokusebenza kweebhetri ze-lithium-ion kunokuchaphazeleka ngamaqondo obushushu aphantsi, ngakumbi lawo asetyenziswa kwizithuthi zombane ezixutyiweyo, izithuthi zombane ezicocekileyo, kunye nezithuthi zombane ezixutyiweyo. Ukuhamba esibhakabhakeni yenye indawo ebandayo efuna iibhetri ze-lithium-ion. Umzekelo, ubushushu kwiMars bunokwehla bufikelele kwi--120 degrees Celsius, nto leyo ebangela umqobo omkhulu ekusebenziseni iibhetri ze-lithium-ion kwi-spacecraft. Ubushushu obuphantsi bokusebenza bunokukhokelela ekunciphiseni izinga lokudluliselwa kwetshaja kunye nomsebenzi wokuphendula ngamakhemikhali kwiibhetri ze-lithium-ion, okubangela ukwehla kwinqanaba lokusasazwa kwee-ion ze-lithium ngaphakathi kwe-electrode kunye nokuqhuba kwe-ionic kwi-electrolyte. Oku kuhla kubangela amandla kunye namandla anciphileyo, kwaye ngamanye amaxesha nokuncipha kokusebenza53.
Isiphumo sobushushu obuphezulu senzeka kwiindawo ezahlukeneyo zokusetyenziswa, kuquka iindawo zobushushu obuphezulu nobuphantsi, ngelixa isiphumo sobushushu obuphantsi sikhawulelwe kwiindawo zokusetyenziswa kobushushu obuphantsi. Isiphumo sobushushu obuphantsi simiselwa ikakhulu bubushushu obuphakathi, ngelixa isiphumo sobushushu obuphezulu sidla ngokunxulunyaniswa ngokuchanekileyo nobushushu obuphezulu ngaphakathi kwebhetri ye-lithium-ion ngexesha lokusebenza.
Iibhetri zeLithium-ion zivelisa ubushushu phantsi kweemeko zamandla aphezulu (kuquka ukutshaja ngokukhawuleza kunye nokukhupha ngokukhawuleza), nto leyo ebangela ukuba ubushushu bangaphakathi bunyuke. Ukuvezwa kubushushu obuphezulu kunokubangela ukuwohloka kokusebenza kwebhetri, kuquka ukulahlekelwa ngumthamo namandla. Ngokwesiqhelo, ukulahleka kwe-lithium kunye nokubuyiselwa kwezinto ezisebenzayo kubushushu obuphezulu kukhokelela ekulahlekelweni ngumthamo, kwaye ukulahleka kwamandla kungenxa yokwanda kokumelana kwangaphakathi. Ukuba ubushushu abulawuleki, kwenzeka ukuba kubekho ukufudumeza okugqithisileyo, okuthi kwezinye iimeko kukhokelela ekutshisweni okuzenzekelayo okanye ekuqhumeni.
Izibalo ze-QSAR yindlela yokubala okanye yokubala yokumisela esetyenziselwa ukuchonga ubudlelwane phakathi komsebenzi webhayoloji kunye neempawu zesakhiwo seekhompawundi. Zonke iimolekyuli eziyilwe zalungiswa kwaye ezinye iimpawu ze-QSAR zabalwa kwinqanaba le-PM6. Itheyibhile 3 idwelisa ezinye zeenkcazo ze-QSAR ezibaliweyo. Imizekelo yezo nkcazo yitshaja, i-TDM, amandla apheleleyo (E), amandla e-ionization (IP), i-Log P, kunye ne-polarizability (jonga iTheyibhile 1 yeefomula zokumisela i-IP kunye ne-Log P).
Iziphumo zokubala zibonisa ukuba itshaja iyonke yazo zonke izakhiwo ezifundweyo yi-zero kuba zikwimeko yomhlaba. Kwithuba lokuqala lokusebenzisana, i-TDM ye-glycerol yayiyi-2.788 Debye kunye ne-6.840 Debye kwi-3PVA-(C10) 2Na Alg, ngelixa amaxabiso e-TDM anyuswe ukuya kwi-17.990 Debye, 8.848 Debye, 5.874 Debye, 7.568 Debye kunye ne-12.779 Debye xa i-3PVA-(C10) 2Na Alg isebenzisana neeyunithi ze-1, 2, 3, 4 kunye ne-5 ze-glycerol, ngokulandelelana. Okukhona ixabiso le-TDM liphezulu, kokukhona i-reactivity yayo iphezulu nokusingqongileyo.
Amandla apheleleyo (E) nawo abaliwe, kwaye amaxabiso e-E e-glycerol kunye ne-3PVA-(C10)2 NaAlg afunyenwe engama--141.833 eV kunye ne--200092.503 eV, ngokwahlukeneyo. Okwangoku, izakhiwo ezimele i-3PVA-(C10)2 NaAlg zisebenzisana neeyunithi ze-glycerol eziyi-1, 2, 3, 4 kunye ne-5; i-E iba yi--996.837, -1108.440, -1238.740, -1372.075 kunye ne--1548.031 eV, ngokwahlukeneyo. Ukwandisa umxholo we-glycerol kukhokelela ekunciphiseni kwamandla apheleleyo kwaye ngenxa yoko kunyuke kwi-reactivity. Ngokusekelwe ekubalweni kwamandla apheleleyo, kwagqitywa kwelokuba i-molecule yemodeli, eyi-3PVA-2Na Alg-5 Gly, iyasebenza ngakumbi kunezinye iimolekyuli zemodeli. Le nto inxulumene nesakhiwo sazo. I-3PVA-(C10)2NaAlg inamaqela amabini kuphela e-COONa, ngelixa ezinye izakhiwo zinamaqela amabini e-COONa kodwa zinamaqela amaninzi e-OH, oko kuthetha ukuba ukusabela kwazo kwindalo esingqongileyo kuyanda.
Ukongeza, amandla e-ionization (IE) azo zonke izakhiwo ayaqwalaselwa kolu phononongo. Amandla e-ionization yiparameter ebalulekileyo yokulinganisa ukwenzeka kwemodeli efundwayo. Amandla afunekayo ukuhambisa i-electron ukusuka kwindawo enye ye-molecule ukuya kwi-infinity abizwa ngokuba yi-ionization energy. Amele inqanaba le-ionization (oko kukuthi ukwenzeka) kwe-molecule. Okukhona amandla e-ionization ephezulu, kokukhona ukwenzeka okuphantsi. Iziphumo ze-IE ze-3PVA-(C10)2NaAlg ezisebenzisana neeyunithi ze-glycerol eziyi-1, 2, 3, 4 kunye ne-5 beziyi--9.256, -9.393, -9.393, -9.248 kunye ne--9.323 eV, ngokwahlukeneyo, ngelixa ii-IE ze-glycerol kunye ne-3PVA-(C10)2NaAlg beziyi--5.157 kunye ne--9.341 eV, ngokwahlukeneyo. Ekubeni ukongezwa kwe-glycerol kubangele ukwehla kwexabiso le-IP, i-reactivity ye-molecular yanda, nto leyo ephucula ukusebenza kwe-PVA/NaAlg/glycerol model molecule kwizixhobo ze-electrochemical.
Inkcazo yesihlanu kwiTheyibhile 3 yiLog P, eyi-logarithm ye-partition coefficient kwaye isetyenziselwa ukuchaza ukuba isakhiwo esifundwayo si-hydrophilic okanye si-hydrophobic na. Ixabiso leLog P elingalunganga libonisa imolekyuli ye-hydrophilic, oko kuthetha ukuba inyibilika lula emanzini kwaye inyibilika kakubi kwi-organic solvents. Ixabiso elilungileyo libonisa inkqubo echaseneyo.
Ngokusekelwe kwiziphumo ezifunyenweyo, kunokugqitywa kwelokuba zonke izakhiwo zinomoya obandayo, kuba ixabiso lazo leLog P (3PVA-(C10)2Na Alg − 1Gly, 3PVA-(C10)2Na Alg − 2Gly, 3PVA-(C10)2Na Alg − 3Gly, 3PVA-(C10)2Na Alg − 4Gly kunye ne3PVA-(C10)2Na Alg − 5Gly) ziyi -3.537, -5.261, -6.342, -7.423 kunye ne -8.504, ngokulandelelana, ngelixa ixabiso leLog P leglycerol liyi -1.081 kuphela kunye ne-3PVA-(C10)2Na Alg liyi -3.100 kuphela. Oku kuthetha ukuba iipropati zesakhiwo esifundwayo ziya kutshintsha njengoko iimolekyuli zamanzi zifakwa kwisakhiwo saso.
Okokugqibela, i-polarizabilities yazo zonke izakhiwo ikwabalwa kwinqanaba le-PM6 kusetyenziswa indlela ye-semi-empirical. Ngaphambili kwaphawulwa ukuba i-polarizability yezinto ezininzi ixhomekeke kwizinto ezahlukeneyo. Eyona nto ibalulekileyo yivolumu yesakhiwo esifundwayo. Kuzo zonke izakhiwo ezibandakanya uhlobo lokuqala lonxibelelwano phakathi kwe-3PVA kunye ne-2NaAlg (unxibelelwano lwenzeka ngenombolo ye-athomu yekhabhoni 10), i-polarizability iphuculwa ngokongezwa kwe-glycerol. I-polarizability iyanda ukusuka kwi-29.690 Å ukuya kwi-35.076, 40.665, 45.177, 50.239 kunye ne-54.638 Å ngenxa yokusebenzisana neeyunithi ze-glycerol eziyi-1, 2, 3, 4 kunye ne-5. Ngoko ke, kufunyenwe ukuba imolekyuli yemodeli ene-polarizability ephezulu yi-3PVA-(C10)2NaAlg−5Gly, ngelixa imolekyuli yemodeli ene-polarizability ephantsi yi-3PVA-(C10)2NaAlg, eyi-29.690 Å.
Uvavanyo lweenkcazo ze-QSAR lubonise ukuba ulwakhiwo olumele i-3PVA-(C10)2NaAlg − 5Gly lolona lusebenzayo kwintsebenziswano yokuqala ecetywayo.
Kwimo yesibini yokusebenzisana phakathi kwe-PVA trimer kunye ne-NaAlg dimer, iziphumo zibonisa ukuba iitshaja zazo ziyafana nezo zicetyisiweyo kwicandelo elidlulileyo kwintsebenziswano yokuqala. Zonke izakhiwo azinatshaja ye-elektroniki, oko kuthetha ukuba zonke zikwimeko yomhlaba.
Njengoko kubonisiwe kwiTheyibhile 4, amaxabiso e-TDM (abalwe kwinqanaba le-PM6) eTheyibhile 1 Na Alg − 3PVA-Mid 1 Na Alg anyuke ukusuka kwi-11.581 Debye ukuya kwi-15.756, 19.720, 21.756, 22.732, 15.507, kunye ne-15.756 xa iTheyibhile 1 Na Alg − 3PVA-Mid 1 Na Alg isabela ngeeyunithi ze-glycerol eziyi-1, 2, 3, 4, 5, kunye nezi-6. Nangona kunjalo, amandla apheleleyo ayancipha ngokwanda kwenani leeyunithi ze-glycerol, kwaye xa iTerm 1 Na Alg − 3PVA- Mid 1 Na Alg idibana nenani elithile leeyunithi ze-glycerol (1 ukuya ku-6), amandla apheleleyo yi-− 996.985, − 1129.013, − 1267.211, − 1321.775, − 1418.964, kunye ne-− 1637.432 eV, ngokwahlukeneyo.
Kwithuba lesibini lokusebenzisana, i-IP, i-Log P kunye ne-polarizability nazo zibalwe kwinqanaba le-PM6 yethiyori. Ke ngoko, baqwalasele iinkcazo ezintathu ezinamandla kakhulu ze-molecular reactivity. Kwizakhiwo ezimele i-End 1 Na Alg-3PVA-Mid 1 Na Alg ezisebenzisana neeyunithi ze-glycerol eziyi-1, 2, 3, 4, 5 kunye ne-6, i-IP iyanda ukusuka kwi-−9.385 eV ukuya kwi-−8.946, −8.848, −8.430, −9.537, −7.997 kunye ne-−8.900 eV. Nangona kunjalo, ixabiso le-Log P elibaliweyo laliphantsi ngenxa yokufakelwa kwe-End 1 Na Alg-3PVA-Mid 1 Na Alg ene-glycerol. Njengoko umxholo we-glycerol unyuka ukusuka ku-1 ukuya ku-6, amaxabiso ayo aba yi--5.334, -6.415, -7.496, -9.096, -9.861 kunye ne--10.53 endaweni ye--3.643. Okokugqibela, idatha ye-polarizability ibonise ukuba ukonyusa umxholo we-glycerol kubangele ukwanda kwe-polarizability ye-Term 1 Na Alg-3PVA-Mid 1 Na Alg. I-polarizability ye-molecule yemodeli I-Term 1 Na Alg-3PVA-Mid 1 Na Alg inyuke ukusuka kwi-31.703 Å ukuya kwi-63.198 Å emva kokusebenzisana neeyunithi ze-glycerol ezi-6. Kubalulekile ukuqaphela ukuba ukonyusa inani leeyunithi ze-glycerol kumathuba okusebenzisana kwesibini kwenziwa ukuqinisekisa ukuba nangona inani elikhulu leeathom kunye nesakhiwo esintsonkothileyo, ukusebenza kusaphucuka ngokwanda komxholo we-glycerol. Ngoko ke, kunokuthiwa imodeli ye-PVA/Na Alg/glycerin ekhoyo inokutshintsha kancinci iibhetri ze-lithium-ion, kodwa uphando nophuhliso olungakumbi luyadingeka.
Ukuchonga amandla okubopha omphezulu kwi-adsorbate kunye nokuvavanya ukusebenzisana okwahlukileyo phakathi kweenkqubo kufuna ulwazi lohlobo lwebhondi ekhoyo phakathi kwazo naziphi na ii-athomu ezimbini, ubunzima bokusebenzisana phakathi kwemolekyuli kunye ne-intramolecular, kunye nokusasazwa koxinano lwe-electron kumphezulu kunye ne-adsorbent. Uxinano lwe-electron kwindawo ebalulekileyo yebhondi (BCP) phakathi kwee-athomu ezisebenzisanayo lubalulekile ekuvavanyeni amandla ebhondi kuhlalutyo lwe-QTAIM. Okukhona uxinano lwe-electron charge luphezulu, kokukhona uxinano lwe-covalent luzinzile kwaye, ngokubanzi, uxinano lwe-electron luphezulu kwezi ndawo zibalulekileyo. Ngaphezu koko, ukuba zombini uxinano lwamandla e-electron iyonke (H(r)) kunye noxinano lwe-Laplace charge (∇2ρ(r)) zingaphantsi kwe-0, oku kubonisa ukubakho kokusebenzisana kwe-covalent (jikelele). Kwelinye icala, xa i-∇2ρ(r) kunye ne-H(r) zingaphezulu kwe-0.54, kubonisa ukubakho kokusebenzisana kwe-non-covalent (igobolondo elivaliweyo) njengezibopho ze-hydrogen ezibuthathaka, amandla e-van der Waals kunye nokusebenzisana kwe-electrostatic. Uhlalutyo lwe-QTAIM lutyhile uhlobo lonxibelelwano olungekho kwi-covalent kwizakhiwo ezifundweyo njengoko kubonisiwe kwiMifanekiso 7 kunye no-8. Ngokusekelwe kuhlalutyo, iimolekyuli zemodeli ezimele i-3PVA − 2Na Alg kunye neTerm 1 Na Alg − 3PVA –Mid 1 Na Alg zibonise uzinzo oluphezulu kuneemolekyuli ezisebenzisana neeyunithi ezahlukeneyo ze-glycine. Oku kungenxa yokuba inani lonxibelelwano olungekho kwi-covalent oluxhaphakileyo kwisakhiwo se-alginate ezifana nonxibelelwano lwe-electrostatic kunye neebhondi ze-hydrogen zivumela i-alginate ukuzinzisa ii-composites. Ngaphezu koko, iziphumo zethu zibonisa ukubaluleka konxibelelwano olungekho kwi-covalent phakathi kweemolekyuli zemodeli ze-3PVA − 2Na Alg kunye neTerm 1 Na Alg − 3PVA –Mid 1 Na Alg kunye ne-glycine, nto leyo ebonisa ukuba i-glycine idlala indima ebalulekileyo ekuguquleni imeko-bume ye-elektroniki iyonke yee-composites.
Uhlalutyo lwe-QTAIM lwemolekyuli yemodeli i-3PVA − 2NaAlg esebenzisana ne-(a) 0 Gly, (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, kunye (f) 5Gly.