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Ngenxa yobuningi bemithombo ye-sodium, amabhethri e-sodium-ion (ama-NIB) amelela ikhambi elithembisayo lokugcinwa kwamandla kagesi. Njengamanje, isithiyo esikhulu ekuthuthukisweni kobuchwepheshe be-NIB ukuntuleka kwezinto ze-electrode ezingagcina/zikhulule ama-ion e-sodium isikhathi eside. Ngakho-ke, inhloso yalolu cwaningo ukuphenya ngokwethiyori umphumela wokwengezwa kwe-glycerol ku-polyvinyl alcohol (PVA) kanye ne-sodium alginate (NaAlg) blends njengezinto ze-NIB electrode. Lolu cwaningo lugxile ezincazelweni ze-electronic, thermal, kanye ne-quantitative structure-activity relationship (QSAR) zama-polymer electrolyte asekelwe ku-PVA, i-sodium alginate, kanye ne-glycerol blends. Lezi zakhiwo ziphenywa kusetshenziswa izindlela ze-semi-empirical kanye ne-density functional theory (DFT). Njengoba ukuhlaziywa kwesakhiwo kwembule imininingwane yokusebenzisana phakathi kwe-PVA/alginate ne-glycerol, kuphenywe amandla e-band gap (Eg). Imiphumela ikhombisa ukuthi ukwengezwa kwe-glycerol kuphumela ekwehleni kwenani le-Eg ku-0.2814 eV. I-molecule electrostatic potential surface (MESP) ikhombisa ukusatshalaliswa kwezifunda ezicebile ngama-electron kanye nama-electron-poor kanye nama-molecule charges ohlelweni lonke lwe-electrolyte. Amapharamitha okushisa afundwe afaka i-enthalpy (H), i-entropy (ΔS), umthamo wokushisa (Cp), amandla amahhala e-Gibbs (G) kanye nokushisa kokwakheka. Ngaphezu kwalokho, izincazelo eziningana zobudlelwano besakhiwo-umsebenzi (QSAR) ezifana ne-total dipole moment (TDM), amandla aphelele (E), amandla e-ionization (IP), i-Log P kanye ne-polarizability kuhlolwe kulolu cwaningo. Imiphumela ibonise ukuthi i-H, i-ΔS, i-Cp, i-G kanye ne-TDM kukhuphuke ngokushisa okwandayo kanye nokuqukethwe kwe-glycerol. Phakathi naleso sikhathi, ukushisa kokwakheka, i-IP kanye ne-E kwehlile, okwathuthukisa ukusabela kanye ne-polarizability. Ngaphezu kwalokho, ngokungeza i-glycerol, i-voltage yeseli ikhuphuke yaya ku-2.488 V. DFT kanye nokubalwa kwe-PM6 okusekelwe kuma-electrolyte asekelwe ku-PVA/Na Alg glycerol asebenzisa izindleko abonisa ukuthi angashintsha amabhethri e-lithium-ion ngokwengxenye ngenxa yokusebenza kwawo okuningi, kodwa kudingeka ukuthuthukiswa okwengeziwe kanye nocwaningo.
Nakuba amabhethri e-lithium-ion (ama-LIB) esetshenziswa kabanzi, ukusetshenziswa kwawo kubhekene nemikhawulo eminingi ngenxa yokuphila kwawo okufushane, izindleko eziphezulu, kanye nokukhathazeka ngokuphepha. Amabhethri e-Sodium-ion (ama-SIB) angaba yindlela engcono kune-LIB ngenxa yokutholakala kwawo kabanzi, izindleko eziphansi, kanye nokungabi nobuthi kwe-sodium element. Amabhethri e-Sodium-ion (ama-SIB) aba uhlelo lokugcina amandla olubaluleke kakhulu lwamadivayisi e-electrochemical1. Amabhethri e-Sodium-ion athembele kakhulu kuma-electrolyte ukuze kube lula ukuthuthwa kwama-ion futhi akhiqize ugesi wamandla2,3. Ama-electrolyte oketshezi akhiwa kakhulu ngosawoti wensimbi kanye nezinyibilikisi eziphilayo. Ukusetshenziswa okusebenzayo kudinga ukucatshangelwa ngokucophelela ukuphepha kwama-electrolyte oketshezi, ikakhulukazi lapho ibhethri libhekene nokucindezeleka kokushisa noma kukagesi4.
Amabhethri e-Sodium-ion (ama-SIB) kulindeleke ukuthi athathe indawo yamabhethri e-lithium-ion maduze nje ngenxa yobuningi bawo bokugcina olwandle, ukungabi nobuthi, kanye nezindleko eziphansi zezinto ezibonakalayo. Ukuhlanganiswa kwezinto ze-nanomaterial kusheshise ukuthuthukiswa kokugcinwa kwedatha, amadivayisi kagesi, kanye nokukhanya. Izincwadi eziningi zibonise ukusetshenziswa kwezakhiwo ezahlukene ze-nano (isb., ama-metal oxides, i-graphene, ama-nanotubes, nama-fullerenes) kumabhethri e-sodium-ion. Ucwaningo lugxile ekuthuthukisweni kwezinto ze-anode, kufaka phakathi ama-polymer, kumabhethri e-sodium-ion ngenxa yokuguquguquka kwawo kanye nobungane bemvelo. Intshisekelo yocwaningo emkhakheni wamabhethri e-polymer aphinde ashajwe izokwanda ngokungangabazeki. Izinto ezintsha ze-polymer electrode ezinezakhiwo nezakhiwo ezihlukile cishe zizovula indlela yobuchwepheshe bokugcina amandla obunobungani nemvelo. Nakuba izinto ezahlukene ze-polymer electrode ziye zahlolwa ukuze zisetshenziswe kumabhethri e-sodium-ion, le nsimu isesezigabeni zayo zokuqala zokuthuthukiswa. Kumabhethri e-sodium-ion, izinto eziningi ze-polymer ezinezilungiselelo ezahlukene zesakhiwo zidinga ukuhlolwa. Ngokusekelwe olwazini lwethu lwamanje mayelana nendlela yokugcina ama-ion e-sodium ezintweni ze-polymer electrode, kungacatshangwa ukuthi amaqembu e-carbonyl, ama-free radicals, nama-heteroatom ohlelweni oluhlanganisiwe angasebenza njengezindawo ezisebenzayo zokuxhumana nama-ion e-sodium. Ngakho-ke, kubalulekile ukuthuthukisa ama-polymer amasha anobuningi obukhulu balezi zindawo ezisebenzayo. I-gel polymer electrolyte (GPE) ubuchwepheshe obuhlukile obuthuthukisa ukuthembeka kwebhethri, ukuqhuba kwe-ion, ukungavuki, ukuguquguquka okuphezulu, kanye nokusebenza okuhle12.
Ama-matrices e-polymer afaka izinto ezifana ne-PVA kanye ne-polyethylene oxide (PEO)13. I-polymer egeleza ngejeli (GPE) ivimba i-electrolyte ewuketshezi ku-polymer matrix, okunciphisa ingozi yokuvuza uma kuqhathaniswa nabahlukanisi bezentengiselwano14. I-PVA iyi-polymer ebolayo yokwenziwa. Inemvume ephezulu, ayibizi futhi ayinabo ubuthi. Le nto yaziwa ngezakhiwo zayo zokwakha ifilimu, ukuzinza kwamakhemikhali kanye nokunamathela. Iphinde ibe namaqembu asebenzayo (OH) kanye nobuningi obuphezulu bokuxhumanisa i-cross-linking15,16,17. Ukuxuba i-polymer, ukwengeza i-plasticizer, ukwengeza okuhlanganisiwe kanye namasu e-polymerization e-in situ asetshenziswe ukuthuthukisa ukuhanjiswa kwe-electrolytes ye-polymer esekelwe ku-PVA ukunciphisa i-crystallinity ye-matrix nokwandisa ukuguquguquka kweketanga18,19,20.
Ukuxuba kuyindlela ebalulekile yokuthuthukisa izinto ze-polymeric zezicelo zezimboni. Izingxube ze-polymer zivame ukusetshenziselwa: (1) ukuthuthukisa izakhiwo zokucubungula zama-polymer emvelo ezisetshenziswa ezimbonini; (2) ukuthuthukisa izakhiwo zamakhemikhali, zomzimba, kanye nezemishini zezinto ezibolayo; kanye (3) ukuzivumelanisa nesidingo esishintsha ngokushesha sezinto ezintsha embonini yokupakisha ukudla. Ngokungafani ne-copolymerization, ukuxuba i-polymer kuyinqubo engabizi kakhulu esebenzisa izinqubo ezilula zomzimba kunezinqubo zamakhemikhali eziyinkimbinkimbi ukufeza izakhiwo ezifiselekayo21. Ukuze kwakhiwe ama-homopolymer, ama-polymer ahlukene angasebenzisana ngamandla e-dipole-dipole, amabhondi e-hydrogen, noma ama-complexes okudlulisa i-charge22,23. Izingxube ezenziwe ngama-polymer emvelo nawenziwe zingahlanganisa ukuhambisana okuhle kwezinto eziphilayo nezakhiwo ezinhle kakhulu zemishini, zidale into engcono kakhulu ngezindleko zokukhiqiza eziphansi24,25. Ngakho-ke, kube nesithakazelo esikhulu ekudaleni izinto ze-polymeric ezihambisana ne-bio ngokuxuba ama-polymer ahlanganisiwe nawemvelo. I-PVA ingahlanganiswa ne-sodium alginate (NaAlg), i-cellulose, i-chitosan kanye ne-starch26.
I-Sodium alginate iyi-polymer yemvelo kanye ne-anionic polysaccharide ekhishwe ku-algae ensundu yasolwandle. I-Sodium alginate iqukethe i-β-(1-4)-linked D-mannuronic acid (M) kanye ne-α-(1-4)-linked L-guluronic acid (G) ehlelwe ngezindlela ze-homopolymeric (poly-M kanye ne-poly-G) kanye nama-heteropolymeric blocks (MG noma GM)27. Okuqukethwe kanye nesilinganiso esihlobene sama-M kanye nama-G blocks kunomthelela omkhulu ezakhiweni zamakhemikhali nezomzimba ze-alginate28,29. I-Sodium alginate isetshenziswa kabanzi futhi ifundwa ngenxa yokubola kwayo, ukuhambisana kwayo nezinto eziphilayo, izindleko eziphansi, izakhiwo ezinhle zokwakha ifilimu, kanye nokungabi nobuthi. Kodwa-ke, inani elikhulu lamaqembu e-free hydroxyl (OH) kanye ne-carboxylate (COO) ku-alginate chain lenza i-alginate ibe ne-hydrophilic kakhulu. Kodwa-ke, i-alginate inezakhiwo ezimbi zemishini ngenxa yobuthakathaka bayo nokuqina kwayo. Ngakho-ke, i-alginate ingahlanganiswa nezinye izinto zokwenziwa ukuze kuthuthukiswe ukuzwela kwamanzi kanye nezakhiwo zemishini30,31.
Ngaphambi kokuklama izinto ezintsha ze-electrode, izibalo ze-DFT zivame ukusetshenziselwa ukuhlola ukuthi kungenzeka yini ukwenziwa kwezinto ezintsha. Ngaphezu kwalokho, ososayensi basebenzisa ukumodela kwama-molecule ukuqinisekisa nokubikezela imiphumela yokuhlola, ukonga isikhathi, ukunciphisa imfucuza yamakhemikhali, nokubikezela ukuziphatha kokuxhumana32. Ukumodela kwama-molecule sekuyinto enamandla futhi ebalulekile yesayensi emikhakheni eminingi, kufaka phakathi isayensi yezinto, izinto ze-nanomaterials, i-computational chemistry, kanye nokutholakala kwezidakamizwa33,34. Besebenzisa izinhlelo zokumodela, ososayensi bangathola ngqo idatha yama-molecule, kufaka phakathi amandla (ukushisa kokwakheka, amandla e-ionization, amandla okusebenza, njll.) kanye ne-geometry (ama-bond engela, ubude be-bond, nama-torsion engela)35. Ngaphezu kwalokho, izakhiwo ze-elekthronikhi (ishaja, amandla e-HOMO kanye ne-LUMO band gap, i-electron affinity), izakhiwo ze-spectral (izindlela zokudlidliza ezihlukile kanye namandla afana ne-FTIR spectra), kanye nezakhiwo ze-bulk (ivolumu, ukusabalala, i-viscosity, i-modulus, njll.)36 zingabalwa.
I-LiNiPO4 ikhombisa izinzuzo ezingaba khona ekuncintisaneni nezinto ze-electrode zebhethri le-lithium-ion ngenxa yobuningi bayo bamandla aphezulu (i-voltage yokusebenza engaba ngu-5.1 V). Ukuze kusetshenziswe ngokugcwele inzuzo ye-LiNiPO4 esifundeni se-voltage ephezulu, i-voltage yokusebenza idinga ukwehliswa ngoba i-electrolyte ye-voltage ephezulu ethuthukisiwe njengamanje ingahlala izinzile kuma-voltage angaphansi kuka-4.8 V. UZhang nabanye baphenye ngokufaka i-doping yazo zonke izinsimbi zokushintsha ze-3d, 4d, kanye ne-5d endaweni ye-Ni ye-LiNiPO4, bakhetha amaphethini okufaka i-doping ngokusebenza okuhle kakhulu kwe-electrochemical, futhi balungisa i-voltage yokusebenza ye-LiNiPO4 ngenkathi begcina ukuzinza kokusebenza kwayo kwe-electrochemical. Ama-voltage aphansi kakhulu okusebenza abawatholile ayengu-4.21, 3.76, kanye no-3.5037 we-Ti, Nb, kanye ne-Ta-doped LiNiPO4, ngokulandelana.
Ngakho-ke, inhloso yalolu cwaningo ukuphenya ngokwethiyori umphumela we-glycerol njenge-plasticizer ezimpahleni ze-elekthronikhi, izincazelo ze-QSAR kanye nezakhiwo zokushisa zesistimu ye-PVA/NaAlg kusetshenziswa izibalo ze-quantum mechanical zokusetshenziswa kwayo kumabhethri e-ion-ion aphinde ashajwe. Ukusebenzisana kwama-molecule phakathi kwemodeli ye-PVA/NaAlg kanye ne-glycerol kuhlaziywe kusetshenziswa i-Bader's quantum atomic theory of molecules (QTAIM).
Imodeli ye-molecule emele ukusebenzisana kwe-PVA ne-NaAlg bese kuba ne-glycerol yenziwe ngcono kusetshenziswa i-DFT. Imodeli yabalwa kusetshenziswa isofthiwe ye-Gaussian 0938 eMnyangweni we-Spectroscopy, iNational Research Center, eCairo, eGibhithe. Amamodeli alungiselelwe kusetshenziswa i-DFT ezingeni le-B3LYP/6-311G(d, p)39,40,41,42. Ukuqinisekisa ukusebenzisana phakathi kwamamodeli afundwe, izifundo zemvamisa ezenziwe ezingeni elifanayo lethiyori zibonisa ukuzinza kwe-geometry elungiselelwe. Ukungabikho kwama-frequency angalungile phakathi kwawo wonke ama-frequency ahlolwe kugqamisa isakhiwo esinqunyiwe ku-minima yangempela enhle ebusweni bamandla angenzeka. Amapharamitha angokwenyama njenge-TDM, amandla e-HOMO/LUMO band gap kanye ne-MESP abalwe ezingeni elifanayo lethiyori ye-quantum mechanical. Ngaphezu kwalokho, amanye amapharamitha okushisa njengokushisa kokugcina kokwakheka, amandla akhululekile, i-entropy, i-enthalpy kanye nomthamo wokushisa kubalwe kusetshenziswa amafomula anikezwe kuThebula 1. Amamodeli afundwe ahlolwe ahluzwa nge-quantum theory yama-athomu kuma-molecule (i-QTAIM) ukuze kutholakale ukusebenzisana okwenzeka ebusweni bezakhiwo ezifundwe. Lokhu kubalwa kwenziwa kusetshenziswa umyalo othi “output=wfn” kukhodi yesofthiwe ye-Gaussian 09 bese kuboniswa kusetshenziswa ikhodi yesofthiwe ye-Avogadro43.
Lapho u-E engamandla angaphakathi, u-P uyingcindezi, u-V uyivolumu, u-Q uyishintshisana lokushisa phakathi kwesistimu nendawo ezungezile, u-T uyizinga lokushisa, u-ΔH uyishintsho lwe-enthalpy, u-ΔG uyishintsho lwamandla amahhala, u-ΔS uyishintsho lwe-entropy, u-a no-b bayimingcele yokudlidliza, u-q uyishaja ye-athomu, kanti u-C uyi-atomic electron density44,45. Ekugcineni, izakhiwo ezifanayo zalungiswa futhi amapharamitha e-QSAR abalwa ezingeni le-PM6 kusetshenziswa i-software code46 ye-SCIGRESS kuMnyango we-Spectroscopy we-National Research Center eCairo, eGibhithe.
Emsebenzini wethu wangaphambilini47, sihlole imodeli engenzeka kakhulu echaza ukusebenzisana kwamayunithi amathathu e-PVA namayunithi amabili e-NaAlg, lapho i-glycerol isebenza njenge-plasticizer. Njengoba kushiwo ngenhla, kunezindlela ezimbili zokuxhumana kwe-PVA ne-NaAlg. Amamodeli amabili, abizwa ngokuthi i-3PVA-2Na Alg (ngokusekelwe kunombolo yekhabhoni 10) kanye ne-Term 1Na Alg-3PVA-Mid 1Na Alg, anenani elincane kakhulu legebe lamandla48 uma kuqhathaniswa nezinye izakhiwo ezicatshangelwe. Ngakho-ke, umphumela wokwengezwa kwe-Gly kumodeli engenzeka kakhulu ye-polymer exubile ye-PVA/Na Alg uhlolwe kusetshenziswa izakhiwo ezimbili zokugcina: i-3PVA-(C10)2Na Alg (ebizwa ngokuthi i-3PVA-2Na Alg ukuze kube lula) kanye ne-Term 1 Na Alg − 3PVA-Mid 1 Na Alg. Ngokusho kwezincwadi, i-PVA, i-NaAlg kanye ne-glycerol kungakha kuphela izibopho ze-hydrogen ezibuthakathaka phakathi kwamaqembu asebenzayo e-hydroxyl. Njengoba kokubili i-PVA trimer kanye ne-NaAlg kanye ne-glycerol dimer kuqukethe amaqembu amaningana e-OH, ukuxhumana kungabonakala ngelinye lamaqembu e-OH. Isibalo 1 sibonisa ukusebenzisana phakathi kwe-molecule ye-glycerol eyimodeli kanye ne-molecule yemodeli i-3PVA-2Na Alg, kanti Isibalo 2 sibonisa imodeli eyakhiwe yokusebenzisana phakathi kwe-molecule yemodeli i-Term 1Na Alg-3PVA-Mid 1Na Alg kanye nokuhlushwa okuhlukile kwe-glycerol.
Izakhiwo ezilungiselelwe: (a) I-Gly kanye ne-3PVA − 2Na Alg zixhumana ne-(b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, kanye ne-(f) 5 Gly.
Izakhiwo ezilungiselelwe zeThemu 1Na Alg- 3PVA –Mid 1Na Alg esebenzisana ne-(a) 1 Gly, (b) 2 Gly, (c) 3 Gly, (d) 4 Gly, (e) 5 Gly, kanye ne-(f) 6 Gly.
Amandla e-electron band gap ayipharamitha ebalulekile okufanele icatshangelwe lapho kufundwa ukusabela kwanoma iyiphi into ye-electrode. Ngoba ichaza ukuziphatha kwama-electron lapho into ibhekana nezinguquko zangaphandle. Ngakho-ke, kubalulekile ukulinganisa amandla e-electron band gap e-HOMO/LUMO kuzo zonke izakhiwo ezifundwe. Ithebula 2 libonisa izinguquko emandleni e-HOMO/LUMO e-3PVA-(C10)2Na Alg kanye ne-Term 1Na Alg − 3PVA-Mid 1Na Alg ngenxa yokwengezwa kwe-glycerol. Ngokusho kwe-ref47, inani le-Eg le-3PVA-(C10)2Na Alg lingu-0.2908 eV, kuyilapho inani le-Eg lesakhiwo libonisa amathuba okuxhumana kwesibili (okungukuthi, i-Term 1Na Alg − 3PVA-Mid 1Na Alg) lingu-0.5706 eV.
Kodwa-ke, kwatholakala ukuthi ukungezwa kwe-glycerol kuholele ekushintsheni okuncane enanini le-Eg le-3PVA-(C10)2Na Alg. Lapho i-3PVA-(C10)2NaAlg isebenzisana namayunithi e-glycerol angu-1, 2, 3, 4 kanye no-5, amanani ayo e-Eg aba ngu-0.302, 0.299, 0.308, 0.289 kanye no-0.281 eV, ngokulandelana. Kodwa-ke, kukhona ukuqonda okubalulekile kokuthi ngemva kokwengeza amayunithi e-glycerol angu-3, ​​inani le-Eg laba lincane kunele-3PVA-(C10)2Na Alg. Imodeli emele ukusebenzisana kwe-3PVA-(C10)2Na Alg enamayunithi e-glycerol amahlanu iyimodeli yokusebenzisana okungenzeka kakhulu. Lokhu kusho ukuthi njengoba inani lamayunithi e-glycerol landa, amathuba okuxhumana nawo ayanda.
Okwamanje, ngenxa yamathuba esibili okusebenzisana, amandla e-HOMO/LUMO ama-molecule emodeli amele i-Term 1Na Alg − 3PVA –Mid 1Na Alg- 1Gly, i-Term 1Na Alg − 3PVA –Mid 1Na Alg- 2Gly, i-Term 1Na Alg − 3PVA –Mid 1Na Alg- 3Gly, i-Term 1Na Alg − 3PVA –Mid 1Na Alg- 4Gly, i-Term 1Na Alg − 3PVA –Mid 1Na Alg- 5Gly kanye ne-Term 1Na Alg − 3PVA –Mid 1Na Alg- 6Gly iba yi-1.343, 1.34 7, 0.976, 0.607, 0.348 kanye ne-0.496 eV, ngokulandelana. Ithebula 2 libonisa amandla e-HOMO/LUMO band gap abaliwe azo zonke izakhiwo. Ngaphezu kwalokho, ukuziphatha okufanayo kwamathuba okuxhumana kweqembu lokuqala kuyaphindwa lapha.
Ithiyori yebhendi ku-solid state physics ithi njengoba igebe lebhendi lezinto ze-electrode lincipha, ukuhanjiswa kwe-elekthronikhi kwezinto kuyanda. Ukudonsa nge-doping kuyindlela evamile yokunciphisa igebe lebhendi lezinto ze-cathode ze-sodium-ion. UJiang nabanye basebenzise i-Cu doping ukuthuthukisa ukuhanjiswa kwe-elekthronikhi kwezinto ezifakwe ungqimba lwe-β-NaMnO2. Besebenzisa izibalo ze-DFT, bathole ukuthi ukudonsa nge-doping kunciphisa igebe lebhendi lezinto kusukela ku-0.7 eV kuya ku-0.3 eV. Lokhu kubonisa ukuthi ukudonsa nge-Cu kuthuthukisa ukuhanjiswa kwe-elekthronikhi kwezinto ze-β-NaMnO2.
I-MESP ichazwa njengamandla okusebenzisana phakathi kokusatshalaliswa kweshaja yama-molecule kanye neshaja eyodwa enhle. I-MESP ibhekwa njengethuluzi elisebenzayo lokuqonda nokuhumusha izakhiwo zamakhemikhali kanye nokusabela. I-MESP ingasetshenziswa ukuqonda izindlela zokusebenzisana phakathi kwezinto ze-polymeric. I-MESP ichaza ukusatshalaliswa kweshaja ngaphakathi kwenhlanganisela efundwayo. Ngaphezu kwalokho, i-MESP inikeza ulwazi mayelana nezindawo ezisebenzayo ezintweni ezifundwayo32. Isithombe 3 sibonisa ama-MESP plots e-3PVA-(C10) 2Na Alg, 3PVA-(C10) 2Na Alg − 1Gly, 3PVA-(C10) 2Na Alg − 2Gly, 3PVA-(C10) 2Na Alg − 3Gly, 3PVA-(C10) 2Na Alg − 4Gly, kanye ne-3PVA-(C10) 2Na Alg − 5Gly ebikezelwe ezingeni le-B3LYP/6-311G(d, p) lethiyori.
Ama-contour e-MESP abalwe nge-B3LYP/6-311 g(d, p) ye-(a) Gly kanye ne-3PVA − 2Na Alg esebenzisana ne-(b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, kanye ne-(f) 5 Gly.
Okwamanje, uMfanekiso 4 ukhombisa imiphumela ebaliwe ye-MESP yeThemu 1Na Alg-3PVA – Mid 1Na Alg, Termu 1Na Alg-3PVA – Mid 1Na Alg-1Gly, Termu 1Na Alg-3PVA – Mid 1Na Alg − 2Gly, Termu 1Na Alg-3PVA – Mid 1Na Alg − 3gly, Termu 1Na Alg-3PVA – Mid 1Na Alg − 4Gly, Termu 1Na Alg-3PVA – Mid 1Na Alg-5gly kanye neThemu 1Na Alg-3PVA – Mid 1Na Alg − 6Gly, ngokulandelana. I-MESP ebaliwe imelelwe njengokuziphatha kwe-contour. Imigqa ye-contour imelelwe ngemibala ehlukene. Umbala ngamunye umele inani elihlukile le-electronegativity. Umbala obomvu ubonisa izindawo ezine-electronegative kakhulu noma ezisabelayo. Okwamanje, umbala ophuzi umele izindawo ezingathathi hlangothi 49, 50, 51 esakhiweni. Imiphumela ye-MESP ibonise ukuthi ukusabela kwe-3PVA-(C10)2Na Alg kwanda ngokwanda kombala obomvu nxazonke kwamamodeli afundwe. Phakathi naleso sikhathi, ukuqina kombala obomvu kumephu ye-MESP ye-Term 1Na Alg-3PVA - Mid 1Na Alg model molecule kwehla ngenxa yokusebenzisana nokuqukethwe okuhlukile kwe-glycerol. Ushintsho ekusabalalisweni kombala obomvu nxazonke kwesakhiwo esiphakanyisiwe lubonisa ukusabela, kuyilapho ukwanda kokuqina kuqinisekisa ukwanda kwe-electronegativity ye-molecule ye-3PVA-(C10)2Na Alg model molecule ngenxa yokwanda kokuqukethwe kwe-glycerol.
I-B3LYP/6-311 g(d, p) ibalwe i-MESP Term ye-1Na Alg-3PVA-Mid 1Na Alg esebenzisana ne-(a) 1 Gly, (b) 2 Gly, (c) 3 Gly, (d) 4 Gly, (e) 5 Gly, kanye (f) 6 Gly.
Zonke izakhiwo eziphakanyisiwe zinemingcele yazo yokushisa efana ne-enthalpy, i-entropy, umthamo wokushisa, amandla amahhala kanye nokushisa okwakheka kubalwa emazingeni okushisa ahlukene kusukela ku-200 K kuya ku-500 K. Ukuze kuchazwe ukuziphatha kwezinhlelo zomzimba, ngaphezu kokufunda ukuziphatha kwazo kwe-elekthronikhi, kuyadingeka futhi ukutadisha ukuziphatha kwazo kokushisa njengomsebenzi wokushisa ngenxa yokusebenzisana kwazo, okungabalwa kusetshenziswa izibalo ezinikezwe kuThebula 1. Ukutadisha la mapharamitha okushisa kubhekwa njengesibonakaliso esibalulekile sokuphendula kanye nokuqina kwezinhlelo ezinjalo zomzimba emazingeni okushisa ahlukene.
Ngokuphathelene ne-enthalpy ye-PVA trimer, iqala isabela ne-NaAlg dimer, bese idlula eqenjini le-OH elixhunywe ku-athomu ye-carbon #10, bese kuthi ekugcineni ibe ne-glycerol. I-Enthalpy iyisilinganiso samandla ohlelweni lwe-thermodynamic. I-Enthalpy ilingana nokushisa okuphelele ohlelweni, okulingana namandla angaphakathi ohlelweni kanye nomkhiqizo womthamo walo kanye nokucindezela. Ngamanye amazwi, i-enthalpy ikhombisa ukuthi kungakanani ukushisa nomsebenzi okungeziwe noma okususiwe ku-substance52.
Isithombe 5 sibonisa izinguquko ze-enthalpy ngesikhathi sokusabela kwe-3PVA-(C10)2Na Alg enamazinga ahlukene e-glycerol. Izifinyezo A0, A1, A2, A3, A4, kanye ne-A5 zimele ama-molecule ayimodeli 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, kanye ne-3PVA-(C10)2Na Alg − 5Gly, ngokulandelana. Isithombe 5a sibonisa ukuthi i-enthalpy iyanda ngokushisa okwandayo kanye nokuqukethwe kwe-glycerol. I-enthalpy yesakhiwo emele i-3PVA-(C10)2NaAlg − 5Gly (okungukuthi, i-A5) ku-200 K ingu-27.966 cal/mol, kuyilapho i-enthalpy yesakhiwo emele i-3PVA-2NaAlg ku-200 K ingu-13.490 cal/mol. Okokugcina, njengoba i-enthalpy inhle, lokhu kusabela kuyi-endothermic.
I-Entropy ichazwa njengesilinganiso samandla angatholakali ohlelweni lwe-thermodynamic oluvaliwe futhi ivame ukubhekwa njengesilinganiso sokuphazamiseka kwesistimu. Isibalo 5b sibonisa ushintsho ku-entropy ye-3PVA-(C10)2NaAlg ngokushisa nokuthi isebenzisana kanjani namayunithi ahlukene e-glycerol. Igrafu ikhombisa ukuthi i-entropy iyashintsha ngokulandelana njengoba izinga lokushisa likhuphuka kusuka ku-200 K kuya ku-500 K. Isibalo 5b sibonisa ngokusobala ukuthi i-entropy yemodeli ye-3PVA-(C10)2Na Alg ivame ukufika ku-200 cal/K/mol ku-200 K ngoba imodeli ye-3PVA-(C10)2Na Alg ibonisa ukuphazamiseka okuncane kwe-lattice. Njengoba izinga lokushisa likhuphuka, imodeli ye-3PVA-(C10)2Na Alg iyaphazamiseka futhi ichaza ukwanda kwe-entropy ngokushisa okwandayo. Ngaphezu kwalokho, kusobala ukuthi isakhiwo se-3PVA-C10 2Na Alg-5 Gly sinenani eliphakeme kakhulu le-entropy.
Ukuziphatha okufanayo kuyabonakala kuMfanekiso 5c, okukhombisa ushintsho kumthamo wokushisa ngokushisa. Umthamo wokushisa yinani lokushisa elidingekayo ukushintsha izinga lokushisa lenani elithile lezinto ngo-1 °C47. Umfanekiso 5c ukhombisa izinguquko kumthamo wokushisa we-molecule yemodeli i-3PVA-(C10)2NaAlg ngenxa yokusebenzisana namayunithi e-glycerol angu-1, 2, 3, 4, kanye no-5. Lesi sibalo sibonisa ukuthi umthamo wokushisa wemodeli i-3PVA-(C10)2NaAlg uyanda ngokulandelana nokushisa. Ukwanda okubonakalayo kumthamo wokushisa ngokushisa okwandayo kubangelwa ukudlidliza kokushisa kwe-phonon. Ngaphezu kwalokho, kunobufakazi bokuthi ukwandisa okuqukethwe kwe-glycerol kuholela ekwandeni kumthamo wokushisa wemodeli i-3PVA-(C10)2NaAlg. Ngaphezu kwalokho, isakhiwo sibonisa ukuthi i-3PVA-(C10)2NaAlg−5Gly inenani eliphakeme kakhulu lomthamo wokushisa uma kuqhathaniswa nezinye izakhiwo.
Amanye amapharamitha afana namandla akhululekile kanye nokushisa kokugcina kokwakheka abalwe ezakhiweni ezifundwe futhi aboniswe kuMfanekiso 5d kanye no-e, ngokulandelana. Ukushisa kokugcina kokwakheka ukushisa okukhishwa noma okumuncwa ngesikhathi sokwakheka kwento emsulwa evela ezintweni zayo ezingaphansi kwengcindezi engaguquki. Amandla akhululekile angachazwa njengempahla efana namandla, okungukuthi, inani lawo lincike enanini lento esimweni ngasinye se-thermodynamic. Amandla akhululekile kanye nokushisa kokwakheka kwe-3PVA-(C10)2NaAlg−5Gly kwakuphansi kakhulu futhi kwakungu--1318.338 kanye no--1628.154 kcal/mol, ngokulandelana. Ngokuphambene nalokho, isakhiwo esimele i-3PVA-(C10)2NaAlg sinamanani aphezulu kakhulu wamandla akhululekile kanye nokushisa kokwakheka kwe--690.340 kanye no--830.673 kcal/mol, ngokulandelana, uma kuqhathaniswa nezinye izakhiwo. Njengoba kuboniswe kuMfanekiso 5, izakhiwo ezahlukene zokushisa ziyashintshwa ngenxa yokusebenzisana ne-glycerol. Amandla akhululekile e-Gibbs awekho, okubonisa ukuthi isakhiwo esiphakanyisiwe sizinzile.
I-PM6 ibale amapharamitha okushisa e-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), kanye ne-3PVA- (C10) 2Na Alg − 5 Gly (imodeli A5), lapho (a) kuyi-enthalpy, (b) i-entropy, (c) umthamo wokushisa, (d) amandla amahhala, kanye (e) nokushisa kokwakheka.
Ngakolunye uhlangothi, imodi yesibili yokusebenzisana phakathi kwe-PVA trimer kanye ne-dimeric NaAlg yenzeka emaqenjini e-terminal kanye ne-middle OH esakhiweni se-PVA trimer. Njengaseqenjini lokuqala, amapharamitha okushisa abalwa kusetshenziswa izinga elifanayo lethiyori. Isibalo 6a-e sibonisa ukwehluka kwe-enthalpy, i-entropy, umthamo wokushisa, amandla amahhala, futhi ekugcineni, ukushisa kokwakheka. Isibalo 6a-c sibonisa ukuthi umthamo we-enthalpy, i-entropy kanye nomthamo wokushisa we-Term 1 NaAlg-3PVA-Mid 1 NaAlg ubonisa ukuziphatha okufanayo neqembu lokuqala lapho lisebenzisana namayunithi e-glycerol angu-1, 2, 3, 4, 5 kanye no-6. Ngaphezu kwalokho, amanani awo akhula kancane kancane ngokushisa okwandayo. Ngaphezu kwalokho, kumodeli ehlongozwayo ye-Term 1 Na Alg − 3PVA-Mid 1 Na Alg, amanani e-enthalpy, entropy kanye nomthamo wokushisa anda ngokwanda kokuqukethwe kwe-glycerol. Izifinyezo B0, B1, B2, B3, B4, B5 kanye ne-B6 zimele izakhiwo ezilandelayo ngokulandelana: Ithemu 1 Na Alg − 3PVA- Mid 1 Na Alg, Ithemu 1 Na Alg- 3PVA- Mid 1 Na Alg − 1 Gly, Ithemu 1 Na Alg- 3PVA- Mid 1 Na Alg − 2gly, Ithemu 1 Na Alg- 3PVA- Mid 1 Na Alg − 3gly, Ithemu 1 Na Alg- 3PVA- Mid 1 Na Alg − 4 Gly, Ithemu 1 Na Alg- 3PVA- Mid 1 Na Alg − 5 Gly kanye nethemu 1 Na Alg- 3PVA- Mid 1 Na Alg − 6 Gly. Njengoba kuboniswe ku-Fig. 6a–c, kusobala ukuthi amanani e-enthalpy, entropy kanye nomthamo wokushisa ayanda njengoba inani lamayunithi e-glycerol landa kusuka ku-1 kuya ku-6.
I-PM6 ibale amapharamitha okushisa e-Term 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), kanye Term 1 Na Alg-3PVA- Mid 1 Na Alg – 6 Gly (imodeli B6), kufaka phakathi (a) i-enthalpy, (b) i-entropy, (c) umthamo wokushisa, (d) amandla amahhala, kanye (e) nokushisa kokwakheka.
Ngaphezu kwalokho, isakhiwo esimele iThemu 1 Na Alg-3PVA- Mid 1 Na Alg-6 Gly sinamanani aphezulu kakhulu e-enthalpy, entropy kanye namandla okushisa uma kuqhathaniswa nezinye izakhiwo. Phakathi kwazo, amanani azo akhuphuke kusuka ku-16.703 cal/mol, 257.990 cal/mol/K kanye no-131.323 kcal/mol kuThemu 1 Na Alg − 3PVA- Mid 1 Na Alg kuya ku-33.223 cal/mol, 420.038 cal/mol/K kanye no-275.923 kcal/mol kuThemu 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly, ngokulandelana.
Kodwa-ke, Izibalo 6d kanye no-e zibonisa ukuncika kokushisa kwamandla akhululekile kanye nokushisa kokugcina kokwakheka (HF). I-HF ingachazwa njengoshintsho lwe-enthalpy olwenzeka lapho kwakheka i-mole eyodwa yento kusuka ezintweni zayo ngaphansi kwezimo zemvelo nezijwayelekile. Kusobala kulesi sibalo ukuthi amandla akhululekile kanye nokushisa kokugcina kokwakheka kwazo zonke izakhiwo ezifundwe kubonisa ukuncika okuqondile ekushiseni, okungukuthi, kuyanda kancane kancane nangokuqondile ngokushisa okwandayo. Ngaphezu kwalokho, lesi sibalo siphinde saqinisekisa ukuthi isakhiwo esimele iThemu 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly sinamandla akhululekile aphansi kakhulu kanye ne-HF ephansi kakhulu. Womabili amapharamitha ehle kusuka ku--758.337 kuya ku--899.741 K cal/mol kuthemu 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly kuya ku--1,476.591 kanye no--1,828.523 K cal/mol. Kusobala emiphumeleni ukuthi i-HF iyancipha ngokwanda kwamayunithi e-glycerol. Lokhu kusho ukuthi ngenxa yokwanda kwamaqembu asebenzayo, ukusabela nakho kuyakhula ngakho-ke kudingeka amandla amancane ukuze kwenziwe ukusabela. Lokhu kuqinisekisa ukuthi i-PVA/NaAlg eyenziwe ngepulasitiki ingasetshenziswa kumabhethri ngenxa yokusabela kwayo okuphezulu.
Ngokuvamile, imiphumela yokushisa ihlukaniswe ngezinhlobo ezimbili: imiphumela yokushisa okuphansi kanye nemiphumela yokushisa okuphezulu. Imiphumela yokushisa okuphansi izwakala kakhulu emazweni atholakala ezindaweni eziphakeme, njengeGreenland, Canada, neRussia. Ebusika, izinga lokushisa lomoya wangaphandle kulezi zindawo lingaphansi kakhulu kwama-degree Celsius angu-0. Isikhathi sokuphila kanye nokusebenza kwamabhethri e-lithium-ion kungathinteka amazinga okushisa aphansi, ikakhulukazi lawo asetshenziswa ezimotweni zikagesi ezihlanganisiwe, ezimotweni zikagesi ezihlanzekile, nasezimotweni zikagesi ezihlanganisiwe. Ukuhamba emkhathini kungenye indawo ebandayo edinga amabhethri e-lithium-ion. Isibonelo, izinga lokushisa eMars lingehla liye kuma-degree Celsius angu-120, okubeka isithiyo esikhulu ekusetshenzisweni kwamabhethri e-lithium-ion emkhathini. Amazinga okushisa aphansi okusebenza angaholela ekwehleni kwesilinganiso sokudluliselwa kweshaja kanye nomsebenzi wokusabela kwamakhemikhali wamabhethri e-lithium-ion, okuholela ekwehleni kwesilinganiso sokusabalalisa kwama-ion e-lithium ngaphakathi kwe-electrode kanye nokuqhuba kwe-ionic ku-electrolyte. Lokhu konakala kuholela ekunciphiseni amandla namandla, futhi ngezinye izikhathi ngisho nokusebenza okuncishisiwe53.
Umphumela wokushisa okuphezulu uvela ezindaweni eziningi zokusetshenziswa, kufaka phakathi izindawo zokushisa eziphakeme neziphansi, kuyilapho umphumela wokushisa okuphansi ukhawulelwe kakhulu ezindaweni zokusetshenziswa zokushisa okuphansi. Umphumela wokushisa okuphansi unqunywa kakhulu yizinga lokushisa elizungezile, kuyilapho umphumela wokushisa okuphezulu uvame ukuhlotshaniswa nokushisa okuphezulu ngaphakathi kwebhethri le-lithium-ion ngesikhathi sokusebenza.
Amabhethri e-lithium-ion akhiqiza ukushisa ngaphansi kwezimo zamandla aphezulu (kufaka phakathi ukushaja okusheshayo nokukhipha ngokushesha), okubangela ukuthi izinga lokushisa langaphakathi likhuphuke. Ukuchayeka emazingeni okushisa aphezulu nakho kungabangela ukwehla kokusebenza kwebhethri, kufaka phakathi ukulahlekelwa amandla namandla. Ngokuvamile, ukulahlekelwa yi-lithium kanye nokubuyiselwa kwezinto ezisebenzayo emazingeni okushisa aphezulu kuholela ekulahlekelweni kwamandla, futhi ukulahlekelwa amandla kungenxa yokwanda kokumelana kwangaphakathi. Uma izinga lokushisa lingalawuleki, kwenzeka ukuqhuma kokushisa, okuthi kwezinye izimo kuholele ekushiseni okuzenzakalelayo noma ngisho nasekuqhumeni.
Izibalo ze-QSAR ziyindlela yokubala noma yokubala esetshenziselwa ukuhlonza ubudlelwano phakathi komsebenzi wezinto eziphilayo kanye nezakhiwo zezakhi zamakhemikhali. Wonke ama-molecule aklanywe alungiselelwe kahle kanti ezinye izakhiwo ze-QSAR zabalwa ezingeni le-PM6. Ithebula 3 libala ezinye zezincazelo ze-QSAR ezibaliwe. Izibonelo zezincazelo ezinjalo yi-charge, i-TDM, amandla aphelele (E), i-ionization potential (IP), i-Log P, kanye ne-polarizability (bheka Ithebula 1 ukuthola amafomula okunquma i-IP kanye ne-Log P).
Imiphumela yokubala ikhombisa ukuthi inani eliphelele lazo zonke izakhiwo ezifundwe liyi-zero njengoba zisesimweni somhlaba. Emathubeni okuqala okusebenzisana, i-TDM ye-glycerol yayingu-2.788 Debye kanye no-6.840 Debye we-3PVA-(C10) 2Na Alg, kuyilapho amanani e-TDM anyuswa aba yi-17.990 Debye, 8.848 Debye, 5.874 Debye, 7.568 Debye kanye no-12.779 Debye lapho i-3PVA-(C10) 2Na Alg isebenzisana namayunithi angu-1, 2, 3, 4 kanye no-5 e-glycerol, ngokulandelana. Uma inani le-TDM liphakeme, kulapho ukusebenza kwayo nemvelo kukhuphuka khona.
Amandla aphelele (E) nawo abalwa, futhi amanani e-E e-glycerol kanye ne-3PVA-(C10)2 NaAlg atholakale engama--141.833 eV kanye ne--200092.503 eV, ngokulandelana. Okwamanje, izakhiwo ezimele i-3PVA-(C10)2 NaAlg zisebenzisana namayunithi e-glycerol angu-1, 2, 3, 4 kanye no-5; i-E iba yi--996.837, -1108.440, -1238.740, -1372.075 kanye ne--1548.031 eV, ngokulandelana. Ukwandisa okuqukethwe kwe-glycerol kuholela ekunciphiseni kwamandla aphelele futhi ngaleyo ndlela kwandise ukusabela. Ngokusekelwe ekubalweni kwamandla aphelele, kwaphethwa ngokuthi i-molecule eyimodeli, eyi-3PVA-2Na Alg-5 Gly, isabela kakhulu kunezinye izi-molecule eziyimodeli. Lesi simo sihlobene nesakhiwo sazo. I-3PVA-(C10)2NaAlg iqukethe amaqembu amabili kuphela e-COONa, kanti ezinye izakhiwo ziqukethe amaqembu amabili e-COONa kodwa ziphethe amaqembu amaningana e-OH, okusho ukuthi ukusabela kwawo endaweni ezungezile kuyanda.
Ngaphezu kwalokho, amandla e-ionization (IE) azo zonke izakhiwo ayacatshangelwa kulolu cwaningo. Amandla e-ionization ayipharamitha ebalulekile yokulinganisa ukusabela kwemodeli efundwe. Amandla adingekayo ukuhambisa i-electron ukusuka endaweni eyodwa ye-molecule iye kokungapheli abizwa ngokuthi amandla e-ionization. Amelela izinga le-ionization (okungukuthi ukusabela) kwe-molecule. Uma amandla e-ionization ephakeme, kulapho ukusabela kwehla khona. Imiphumela ye-IE ye-3PVA-(C10)2NaAlg esebenzisana namayunithi e-glycerol angu-1, 2, 3, 4 kanye no-5 yayingu--9.256, -9.393, -9.393, -9.248 kanye no--9.323 eV, ngokulandelana, kuyilapho ama-IE e-glycerol kanye ne-3PVA-(C10)2NaAlg ayengu--5.157 kanye no--9.341 eV, ngokulandelana. Njengoba ukwengezwa kwe-glycerol kuholele ekwehleni kwenani le-IP, ukusabela kwama-molecule kwanda, okuthuthukisa ukusebenza kwe-molecule yemodeli ye-PVA/NaAlg/glycerol kumadivayisi e-electrochemical.
Isichazi sesihlanu kuThebula 3 yiLog P, okuyi-logarithm ye-partition coefficient futhi isetshenziselwa ukuchaza ukuthi isakhiwo esifundwayo si-hydrophilic noma si-hydrophobic. Inani le-Log P elingalungile libonisa i-molecule e-hydrophilic, okusho ukuthi incibilika kalula emanzini futhi incibilike kabi ezinyibilikisini eziphilayo. Inani elihle libonisa inqubo ephambene.
Ngokusekelwe emiphumeleni etholakele, kungaphethwa ngokuthi zonke izakhiwo zinomoya opholile emanzini, njengoba amanani azo e-Log P ​​(3PVA-(C10)2Na Alg − 1Gly, 3PVA-(C10)2Na Alg − 2Gly, 3PVA-(C10)2Na Alg − 3Gly, 3PVA-(C10)2Na Alg − 4Gly kanye ne-3PVA-(C10)2Na Alg − 5Gly) angama--3.537, -5.261, -6.342, -7.423 kanye ne--8.504, ngokulandelana, kuyilapho inani le-Log P le-glycerol lingu--1.081 kuphela kanye ne-3PVA-(C10)2Na Alg lingu--3.100 kuphela. Lokhu kusho ukuthi izakhiwo zesakhiwo esifundwayo zizoshintsha njengoba ama-molecule amanzi efakwa esakhiweni saso.
Okokugcina, i-polarizability yazo zonke izakhiwo nayo ibalwa ezingeni le-PM6 kusetshenziswa indlela ye-semi-empirical. Kwaphawulwa ngaphambilini ukuthi i-polarizability yezinto eziningi incike ezintweni ezahlukahlukene. Isici esibaluleke kakhulu yivolumu yesakhiwo esifundwayo. Kuzo zonke izakhiwo ezihilela uhlobo lokuqala lokuxhumana phakathi kwe-3PVA ne-2NaAlg (ukuxhumana kwenzeka ngenombolo ye-athomu yekhabhoni 10), i-polarizability iyathuthukiswa ngokufakwa kwe-glycerol. I-polarizability iyanda kusuka ku-29.690 Å kuya ku-35.076, 40.665, 45.177, 50.239 kanye no-54.638 Å ngenxa yokusebenzisana namayunithi e-glycerol angu-1, 2, 3, 4 kanye no-5. Ngakho-ke, kwatholakala ukuthi i-molecule eyimodeli ene-polarizability ephezulu kakhulu yi-3PVA-(C10)2NaAlg−5Gly, kuyilapho i-molecule eyimodeli ene-polarizability ephansi kakhulu iyi-3PVA-(C10)2NaAlg, okungu-29.690 Å.
Ukuhlolwa kwezincazelo ze-QSAR kwembule ukuthi isakhiwo esimele i-3PVA-(C10)2NaAlg − 5Gly yisona esisabela kakhulu ekusebenzisaneni kokuqala okuphakanyisiwe.
Kwimodi yesibili yokusebenzisana phakathi kwe-PVA trimer kanye ne-NaAlg dimer, imiphumela ikhombisa ukuthi izindleko zazo zifana nalezo eziphakanyisiwe esigabeni esedlule sokusebenzisana kokuqala. Zonke izakhiwo azinazo i-electronic charge, okusho ukuthi zonke zisesimweni somhlaba.
Njengoba kuboniswe kuThebula 4, amanani e-TDM (abalwe ezingeni le-PM6) eThemu 1 Na Alg − 3PVA-Mid 1 Na Alg akhuphuke kusuka ku-11.581 Debye kuya ku-15.756, 19.720, 21.756, 22.732, 15.507, kanye no-15.756 lapho iThemu 1 Na Alg − 3PVA-Mid 1 Na Alg isabela ngamayunithi angu-1, 2, 3, 4, 5, kanye no-6 e-glycerol. Kodwa-ke, amandla aphelele ayancipha ngokwanda kwenani lamayunithi e-glycerol, futhi lapho i-Term 1 Na Alg − 3PVA- Mid 1 Na Alg ixhumana nenani elithile lamayunithi e-glycerol (1 kuya ku-6), amandla aphelele angu-− 996.985, − 1129.013, − 1267.211, − 1321.775, − 1418.964, kanye no-− 1637.432 eV, ngokulandelana.
Kumathuba okusebenzisana kwesibili, i-IP, i-Log P kanye ne-polarizability nakho kubalwa ezingeni le-PM6 lethiyori. Ngakho-ke, bacabangele izincazelo ezintathu ezinamandla kakhulu ze-reactivity yama-molecule. Ngezakhiwo ezimele i-End 1 Na Alg-3PVA-Mid 1 Na Alg ezisebenzisana namayunithi e-glycerol angu-1, 2, 3, 4, 5 kanye no-6, i-IP iyanda kusuka ku-−9.385 eV kuya ku-−8.946, −8.848, −8.430, −9.537, −7.997 kanye no-−8.900 eV. Kodwa-ke, inani le-Log P elibaliwe laliphansi ngenxa yokwenziwa kwe-plasticization kwe-End 1 Na Alg-3PVA-Mid 1 Na Alg ene-glycerol. Njengoba okuqukethwe kwe-glycerol kukhuphuka kusuka ku-1 kuya ku-6, amanani ayo aba yi--5.334, -6.415, -7.496, -9.096, -9.861 kanye no--10.53 esikhundleni se--3.643. Ekugcineni, idatha ye-polarizability ibonise ukuthi ukwandisa okuqukethwe kwe-glycerol kuholele ekwandeni 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 ikhuphuke kusuka ku-31.703 Å kuya ku-63.198 Å ngemuva kokuxhumana namayunithi ayi-6 e-glycerol. Kubalulekile ukuqaphela ukuthi ukwandisa inani lamayunithi e-glycerol kumathuba okusebenzisana kwesibili kwenziwa ukuqinisekisa ukuthi naphezu kwenani elikhulu lama-athomu nesakhiwo esiyinkimbinkimbi, ukusebenza kusathuthuka ngokwanda kokuqukethwe kwe-glycerol. Ngakho-ke, kungashiwo ukuthi imodeli ye-PVA/Na Alg/glycerin etholakalayo ingathatha indawo yamabhethri e-lithium-ion ngokwengxenye, kodwa kudingeka ucwaningo olwengeziwe kanye nentuthuko.
Ukuchaza amandla okubopha ubuso kuya ku-adsorbate nokuhlola ukusebenzisana okuhlukile phakathi kwezinhlelo kudinga ulwazi lohlobo lwesibopho esikhona phakathi kwama-athomu amabili, ubunzima bokuxhumana phakathi kwama-molecule nangaphakathi kwama-molecule, kanye nokusatshalaliswa kobuningi bama-electron ebusweni kanye ne-adsorbent. Ubuningi bama-electron endaweni ebalulekile yesibopho (i-BCP) phakathi kwama-athomu asebenzisanayo kubalulekile ekuhloleni amandla esibopho ekuhlaziyweni kwe-QTAIM. Uma ubukhulu be-electron charge buphakeme, kulapho ukusebenzisana kwe-covalent kuzinza khona, futhi ngokuvamile, kulapho ubukhulu be-electron buphakeme khona kula maphuzu abalulekile. Ngaphezu kwalokho, uma kokubili ubukhulu bamandla e-electron (i-H(r)) kanye nobuningi be-Laplace charge (∇2ρ(r)) bungaphansi kuka-0, lokhu kubonisa ukuba khona kokuxhumana kwe-covalent (jikelele). Ngakolunye uhlangothi, lapho i-∇2ρ(r) kanye ne-H(r) zinkulu kuno-0.54, kubonisa ukuba khona kokuxhumana okungeyona i-covalent (igobolondo elivaliwe) njengezibopho ze-hydrogen ezibuthakathaka, amandla e-van der Waals kanye nokusebenzisana kwe-electrostatic. Ukuhlaziywa kwe-QTAIM kwembule uhlobo lokuxhumana okungekhona kwe-covalent ezakhiweni ezifundwe njengoba kuboniswe kuZithombe 7 no-8. Ngokusekelwe ekuhlaziyweni, ama-molecule ayimodeli amele i-3PVA − 2Na Alg kanye ne-Term 1 Na Alg − 3PVA –Mid 1 Na Alg abonise ukuzinza okuphezulu kunama-molecule asebenzisana namayunithi ahlukene e-glycine. Lokhu kungenxa yokuthi inani lokuxhumana okungekhona kwe-covalent okuvame kakhulu esakhiweni se-alginate njengokuxhumana kwe-electrostatic kanye nezibopho ze-hydrogen kwenza i-alginate izinze ama-composite. Ngaphezu kwalokho, imiphumela yethu ikhombisa ukubaluleka kokuxhumana okungekhona kwe-covalent phakathi kwama-molecule ayimodeli ye-3PVA − 2Na Alg kanye ne-Term 1 Na Alg − 3PVA –Mid 1 Na Alg kanye ne-glycine, okubonisa ukuthi i-glycine idlala indima ebalulekile ekuguquleni indawo yonke ye-elekthronikhi yama-composite.
Ukuhlaziywa kwe-QTAIM kwe-molecule yemodeli i-3PVA − 2NaAlg esebenzisana ne-(a) 0 Gly, (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, kanye (f) 5Gly.