Ngiyathokoza ngokuvakatjhela i-nature.com. Inguqulo yesiphequluli oyisebenzisako inesekelo elilinganiselwe le-CSS. Ukuze uthole isipiliyoni esihle, sincoma ukusebenzisa inguqulo yakamuva yesiphequluli (nofana ukuvala imodi yokuhambisana ku-Internet Explorer). Phezu kwalokho, ukuqinisekisa ukusekelwa okuragela phambili, isayithi le angeze yafaka iintayela nofana i-JavaScript.
Ngebanga lomthombo omnengi we-sodium, amabhetri we-sodium-ion (ama-NIB) ajamele enye indlela ethembisako yokugcina amandla we-elekthrokhemikhali. Njenganje, isiqabo esikhulu ekuthuthukisweni kwethekhnoloji ye-NIB kutlhogeka kwezinto ze-electrode ezingagcina/zikhuphe ama-ayoni we-sodium isikhathi eside. Ngalokho-ke, umnqopho waloluphenyo kuphenya ngokwethiyori umphumela wokungezwa kwe-glycerol ku-polyvinyl alcohol (PVA) kanye ne-sodium alginate (NaAlg) njengezinto ze-NIB electrode. Irhubhululo leli lidzimelele ekuhlolweni kwe-elekthronikhi, ukutjhisa, kanye nobuhlobo besakhiwo nomsebenzi (i-QSAR) ezihlathulula ama-electrolyte we-polymer asekelwe ku-PVA, i-sodium alginate, kanye ne-glycerol blends. Iimfanelo lezi ziphenywa kusetjenziswa iindlela eziqakathekileko kanye nethiyori yokusebenza kwe-density (DFT). Njengombana ukuhlaziywa kwesakhiwo kuveze imininingwana yokuthintana hlangana kwe-PVA/alginate ne-glycerol, i-band gap energy (Eg) yaphenywa. Imiphumela itjengisa bona ukungezelelwa kwe-glycerol kuphumela ekwehleni kwenani le-Eg ukuya ku-0.2814 eV. I-molecular electrostatic potential surface (MESP) itjengisa ukusabalala kweendawo ezinothileko nama-elekthronikhi kanye namatjhaji wamamolekhyuli kiyo yoke ihlelo le-electrolyte. Amapharamitha womtjhiso afundwako afaka hlangana i-enthalpy (H), i-entropy (ΔS), i-heat capacity (Cp), i-Gibbs free energy (G) kanye ne-heat of formation. Ukungezelela, iinhlathululo ezinengi ezifana ne-total dipole moment (TDM), amandla woke (E), i-ionization potential (IP), i-Log P kanye ne-polarizability kwaphenywa esifundweni lesi. Imiphumela itjengisa bona i-H, ΔS, Cp, G kanye ne-TDM zanda ngokukhula kwamazinga womtjhiso kanye nokuqukethwe kwe-glycerol. Khatheso, ukutjhisa kokwakheka, i-IP ne-E kwehla, okwenza ngcono ukuphendula nokutjhuguluka. Ukungezelela, ngokungezelela i-glycerol, ivoltheji yamaseli ikhuphuke yaba yi-2.488 V. I-DFT kanye ne-PM6 ukubalwa okusekelwe kuma-electrolyte we-PVA/Na Alg glycerol-based ebizako kutjengisa bona angathatha indawo yamabhetri we-lithium-ion ngebanga lokusebenza kwawo, kodwana kutlhogeka ukuthuthukiswa okungeziweko nokurhubhulula.
Nanyana amabhetri we-lithium-ion (ama-LIB) asetjenziswa khulu, ukusetjenziswa kwawo kuqalene nemikhawulo eminengi ngebanga lokuphila kwawo okufitjhani, iindleko eziphezulu, kanye nokutshwenyeka ngokuphepha. Amabhetri we-sodium-ion (ama-SIB) angaba yindlela ehlukileko yokusebenzisa ama-LIB ngebanga lokutholakala kwawo okukhulu, iindleko eziphasi, nokungabi nobuthi be-elementi ye-sodium. Amabhetri we-sodium-ion (ama-SIB) aya ngokuba lihlelo lokugcina amandla eliqakatheke khulu kumadivayisi we-elekthrokhemikhali1. Amabhetri we-sodium-ion athembele khulu kuma-electrolytes ukwenza lula ukuthuthwa kwe-ion nokukhiqiza igezi2,3. Ama-electrolyte amanzi akhiwa khulu ziintswayi zensimbi kanye nama-organic solvents. Ukusetjenziswa okusebenzako kutlhoga ukucabangela ngokucophelela ukuphepha kwama-electrolyte amanzi, khulukhulu lokha ibhetri nayibekelwe ukugandeleleka kokutjhisa nofana kwegezi4.
Amabhetri we-sodium-ion (ama-SIB) kulindeleke bona athathe isikhundla samabhetri we-lithium-ion esikhathini esizako ngebanga lamarekhodi wawo amanengi elwandle, ukungabi nobuthi, kanye neendleko eziphasi zezinto. Ukuhlanganiswa kwama-nanomaterials kukhawulezise ukuthuthukiswa kwedatha, amadivayisi we-elekthronikhi, kanye nama-optical. Iincwadi ezinengi zitjengise ukusetjenziswa kwama-nanostructures ahlukahlukeneko (isib., ama-metal oxides, i-graphene, ama-nanotubes, kanye nama-fullerenes) emabhetri we-sodium-ion. Irhubhululo ligxile ekuthuthukisweni kwezinto ze-anode, okufaka hlangana ama-polymer, wamabhetri we-sodium-ion ngebanga lokusetjenziswa kwawo nobungani bebhoduluko. Ukuthakazelela irhubhululo emkhakheni wamabhetri we-polymer atjhatjhiswako ngokungangabazeki kuzokwanda. Iinsetjenziswa ezitjha ze-polymer electrode ezinezakhiwo ezihlukileko kanye nezakhiwo kungenzeka zivule indlela yobuchwepheshe bokugcina amandla obunobungani bebhoduluko. Nanyana izinto ezihlukahlukeneko ze-polymer electrode zihlolwe ukusetjenziswa emabhetri we-sodium-ion, umkhakha lo usesesigabeni sokuthoma sokuthuthukiswa. Emabhetri we-sodium-ion, izinto ezinengi ze-polymer ezinesakhiwo esihlukileko zitlhoga ukuhlolwa. Ngokuya ngolwazi lwethu lwamanje lwendlela yokugcina ama-ayoni we-sodium eentweni ze-polymer electrode, kungacatshangelwa bona amaqembu we-carbonyl, ama-free radicals, nama-heteroatoms erherhweni elihlanganisiweko angasebenza njengeendawo ezisebenzako zokusebenzisana nama-ayoni we-sodium. Ngalokho-ke, kuqakathekile ukuthuthukisa ama-polymer amatjha ane-density ephezulu yeendawo ezisebenzako. I-Gel polymer electrolyte (GPE) yithekhnoloji ehlukileko eyenza ngcono ukuthembeka kwebhetri, ukudlulisa i-ion, ukungavuzi, ukuguquguquka okukhulu, nokusebenza kuhle12.
Ama-polymer matrices afaka hlangana izinto ezifana ne-PVA kanye ne-polyethylene oxide (PEO)13. I-gel permeable polymer (GPE) yenza bona i-electrolyte emanzini ingakhambi ku-polymer matrix, okunciphisa ubungozi bokuvuza nayiqathaniswa nama-separator wokuthengisa14. I-PVA yi-polymer ebolako eyenziwe ngezinto eziphilako. Ine-permittivity ephezulu, ayibizi begodu ayinabuthi. Into le yaziwa ngezakhiwo zayo zokwenza ifilimu, ukuzinza kwamakhemikhali nokunamathelana. Ibuye ibe namaqembu asebenzako (OH) kanye nokuminyana okuphezulu kokuhlanganisa15,16,17. Ukuhlanganiswa kwe-polymer, ukungezelelwa kwe-plasticizer, ukungezelelwa kwe-composite kanye namaqhinga wokwenza i-polymer in situ kusetjenziselwe ukwenza ngcono ukudluliswa kwama-electrolyte we-polymer asekelwe ku-PVA ukwehlisa ubukristalu be-matrix nokukhuphula ukuguquguquka kweketango18,19,20.
Ukuhlanganisa yindlela eqakathekileko yokuthuthukisa izinto ze-polymeric zokusetjenziswa emabubulweni. Iinhlanganisela zamapholima zivame ukusetjenziselwa: (1) ukwenza ngcono izakhiwo zokucubungula zamapholima wemvelo eensetjenzisweni zebubulo; (2) ukwenza ngcono izakhiwo zamakhemikhali, ezibonakalako, nezomtjhini zezinto ezibolako; begodu (3) ukutjhuguluka ekufuneni okutjhuguluka msinyana kwezinto ezitjha embonini yokupakisha ukudla. Ngokungafani ne-copolimerization, ukuhlanganiswa kwe-polymer yindlela ebiza kancani esebenzisa iindlela ezilula eziphathekako kunokobana kusetjenziswe iindlela ezihlukahlukeneko zamakhemikhali ukufikelela iimpawu ezifunwako21. Ukwenza ama-homopolymer, ama-polymer ahlukileko angasebenzisana ngamandla we-dipole-dipole, amabhondi we-hydrogen, nofana ama-charge-transfer complexes22,23. Iinhlanganisela ezenziwe ngama-polymer wemvelo nezokwenziwa zingahlanganisa ukuhambisana okuhle kwezinto eziphilako kanye nezakhiwo ezihle khulu zemitjhini, okwenza izinto ezihle khulu ngeendleko eziphasi zokukhiqiza24,25. Ngalokho-ke, kube nentshisekelo ekulu ekwenzeni izinto eziphathelene nezinto eziphilako ngokuhlanganisa amapholimeri wokwenziwa newemvelo. I-PVA ingahlanganiswa ne-sodium alginate (NaAlg), i-cellulose, i-chitosan kanye ne-starch26.
I-sodium alginate yi-polymer yemvelo kanye ne-anionic polysaccharide ekhutjhwe e-algae ensundu yelwandle. I-sodium alginate ine-β-(1-4)-linked D-mannuronic acid (M) kanye ne-α-(1-4)-linked L-guluronic acid (G) ehlelwe yaba mafomu we-homopolymeric (i-poly-M kanye ne-poly-G) kanye namabhlogo we-heteropolymeric (MG nofana i-GM)27. Okuqukethwe kanye nesilinganiso esihlobeneko samabhlogo we-M ne-G kunomthelela omkhulu emakhemikhali nezinto eziphathekako ze-alginate28,29. I-sodium alginate isetjenziswa khulu begodu ifundwa ngebanga lokubola kwayo, ukuvumelana kwayo, iindleko eziphasi, izakhiwo ezihle zokwenza amafilimu, nokungabi nobuthi. Kodwana, inani elikhulu lama-hydroxyl (OH) kanye nama-carboxylate (COO) wamaqembu ku-alginate chain kwenza i-alginate ibe yi-hydrophilic ephezulu. Kodwana, i-alginate inezinto ezimbi ngebanga lokuphuka kwayo nokuqina kwayo. Ngalokho-ke, i-alginate ingahlanganiswa nezinye izinto zokwenziwa ukwenza ngcono ukuzwela kwamanzi kanye nezakhiwo zemishini30,31.
Ngaphambi kokuklama izinto ezitjha ze-electrode, ukubalwa kwe-DFT kuvamise ukusetjenziswa ukuhlola ukusebenza kwezinto ezitjha. Ukungezelela, abososayensi basebenzisa ukumodela kwamamolekhyuli ukuqinisekisa nokubikezela imiphumela yokuhlola, ukonga isikhathi, ukwehlisa ukulahlwa kwamakhemikhali, nokubikezela ukuziphatha kokusebenzisana32. Ukumodela kwamamolekhyuli sekuyigatsha elinamandla neliqakathekileko lesayensi emikhakheni eminengi, kufaka hlangana isayensi yezinto, i-nanomaterials, ikhemistri yekhomphyutha, nokutholakala kwemithi33,34. Ngokusebenzisa amahlelo wokwenza imodeli, abososayensi bangathola idatha yamamolekhyuli, kufaka hlangana amandla (ukutjhisa kokwakheka, amandla we-ionization, amandla wokusebenza, njll.) kanye nejometri (ama-engeli wokubopha, ubude bokubopha, kanye nama-engeli wokugoqa)35. Ukungezelela, izakhiwo ze-elekthronikhi (i-charge, i-HOMO kanye ne-LUMO band gap energy, ukuhlobana kwe-elekthronikhi), izakhiwo ze-spectral (iindlela zokudlidliza ezifana namandla we-FTIR spectra), kanye nezakhiwo ze-bulk (umthamo, ukusabalala, ukuthamba, imodyuli, njll.)36 zingabalwa.
I-LiNiPO4 itjengisa iinzuzo ezingaba khona ekuncintisaneni nezinto ze-electrode ezihle zebhetri ye-lithium-ion ngebanga lokuminyana kwamandla aphezulu (ivoltheji yokusebenza engaba ngu-5.1 V). Ukusebenzisa ngokuzeleko inzuzo ye-LiNiPO4 endaweni enevoltheji ephezulu, ivoltheji yokusebenza idinga ukwehliswa ngombana i-electrolyte yevoltheji ephezulu ethuthukisiweko njengamanje ingahlala izinzile kwaphela kumavoltheji angaphasi kwe-4.8 V. Zhang et al. waphenya ukufakwa kwawo woke ama-3d, 4d, kanye nama-5d weensimbi zokutjhuguluka endaweni ye-Ni ye-LiNiPO4, wakhetha amaphetheni wokufakwa ngokusebenza okuhle khulu kwe-elekthrokhemikhali, begodu walungisa ivoltheji yokusebenza ye-LiNiPO4 ngesikhathi kugcinwa ukuzinza okuhlobeneko kokusebenza kwayo kwe-elekthrokhemikhali. Amavoltheji wokusebenza aphasi khulu abawatholileko bekuyi-4.21, 3.76, kanye ne-3.5037 ye-Ti, Nb, kanye ne-Ta-doped LiNiPO4, ngokulandelana.
Ngalokho-ke, umnqopho waloluphenyo kuphenya ngokwethiyori umphumela we-glycerol njengepulasitiki ezakhiweni ze-elekthronikhi, iinhlathululo ze-QSAR kanye nezakhiwo zokutjhisa zesistimu ye-PVA/NaAlg kusetjenziswa ukubalwa kwe-quantum mechanical ukusetjenziswa kwayo emabhetri we-ion-ion atjhatjhiswako. Ukusebenzisana kwamamolekhyuli hlangana nemodeli ye-PVA/NaAlg ne-glycerol kwahlaziywa kusetjenziswa i-Bader's quantum atomic theory of molecules (QTAIM).
Imodeli ye-molecule ejamele ukusebenzisana kwe-PVA ne-NaAlg bese kuthi nge-glycerol yenziwa ngcono ngokusebenzisa i-DFT. Imodeli yabalwa kusetjenziswa isofthiwe ye-Gaussian 0938 eMnyangweni we-Spectroscopy, e-National Research Center, e-Cairo, e-Egypt. Amamodeli alungiswa ngokusebenzisa i-DFT ku-B3LYP/6-311G(d, p) level39,40,41,42. Ukuqinisekisa ukusebenzisana hlangana namamodeli afundwako, iimfundo zamafrikhwensi ezenziwe ezingeni elifanako lethiyori zitjengisa ukuzinza kwejometri elungisiweko. Ukungabi khona kwamafrikhwensi angakalungi hlangana nawo woke amafrikhwensi ahloliweko kuveza isakhiwo esiphethweko ema-minima amahle wamambala ebusweni bamandla angaba khona. Imingcele ebonakalako efana ne-TDM, i-HOMO/LUMO band gap energy kanye ne-MESP zabalwa ngezinga elifanako le-quantum mechanical lethiyori. Ukungezelela, amanye amapharamitha womtjhiso afana nokutjhisa kokugcina kokwakheka, amandla wamahhala, i-entropy, i-enthalpy kanye nomthamo womtjhiso abalwa kusetjenziswa amafomula anikelwe kuThebuli 1. Amamodeli afundwako ahlaziywa ngaphasi kwe-quantum theory of atoms in molecules (QTAIM) ukuhlaziywa ukwenzela ukukhomba ukusebenzisana okwenzeka ebusweni bezakhiwo ezifundwako. Iimbalo lezi zenziwa kusetjenziswa umyalo othi "output=wfn" kukhodi yesofthiwe ye-Gaussian 09 bese zibonwa kusetjenziswa ikhodi yesofthiwe ye-Avogadro43.
Lapho u-E amandla wangaphakathi, u-P umfutho, u-V uyivolumu, u-Q ukutjhuguluka kokutjhisa hlangana nehlelo nebhoduluko layo, u-T uyizinga lokutjhisa, i-ΔH kutjhuguluka kwe-enthalpy, i-ΔG kutjhuguluka kwamandla wamahhala, i-ΔS kutjhuguluka kwe-entropy, a no-b ngamapharamitha wokudlidliza, u-q ngamandla we-athomu, begodu u-C ngamazinyo we-elekthronikhi ye-elekthronikhi, 445. Ekugcineni, izakhiwo ezifanako zalungiswa begodu amapharamitha we-QSAR abalwa ezingeni le-PM6 kusetjenziswa ikhodi yesofthiwe ye-SCIGRESS46 eMnyangweni we-Spectroscopy we-National Research Center e-Cairo, e-Egypt.
Emsebenzini wethu odlulileko47, sihlole imodeli engenzeka khulu echaza ukusebenzisana kwamayunithi amathathu we-PVA namayunithi amabili we-NaAlg, nge-glycerol esebenza njengeplastiki. Njengombana kutjhiwo ngehla, kuneendlela ezimbili zokusebenzisana kwe-PVA ne-NaAlg. Amamodeli amabili, abizwa ngokuthi yi-3PVA-2Na Alg (ngokuya ngenomboro yekhabhoni 10) kanye neThemu 1Na Alg-3PVA-Mid 1Na Alg, anenani elincani khulu lesikhala samandla48 nayiqathaniswa nezinye izakhiwo ezicatshangelweko. Ngalokho-ke, umphumela wokungezelelwa kwe-Gly kumodeli engenzeka khulu ye-PVA/Na Alg blend polymer kwaphenywa kusetjenziswa izakhiwo ezimbili zokugcina: 3PVA-(C10)2Na Alg (ebizwa ngokuthi yi-3PVA-2Na Alg ukuze kube lula) kanye neThemu 1 Na Alg − 3PVA-Mid 1 Na Alg. Ngokuya ngeencwadi, i-PVA, i-NaAlg kanye ne-glycerol zingenza amabhondi we-hydrogen abuthakathaka hlangana namaqembu asebenzako we-hydroxyl. Njengombana zombili i-PVA trimer kanye ne-NaAlg ne-glycerol dimer ziqukethe amaqembu amanengi we-OH, ukuthintana kungenzeka ngelinye lamaqembu we-OH. Umfanekiso 1 utjengisa ukusebenzisana hlangana kwe-glycerol molecule yemodeli kanye ne-model molecule 3PVA-2Na Alg, begodu umfanekiso 2 utjengisa imodeli eyakhiweko yokusebenzisana hlangana ne-model molecule Term 1Na Alg-3PVA-Mid 1Na Alg kanye namazinga ahlukileko we-glycerol.
Izakhiwo ezilungisiweko: (a) i-Gly ne-3PVA − 2Na Alg zisebenzisana (b) ne-1 Gly, (c) i-2 Gly, (d) i-3 Gly, (e) i-4 Gly, kanye (f) ne-5 Gly.
Izakhiwo ezilungisiweko ze-Term 1Na Alg- 3PVA –Mid 1Na Alg ezisebenzisana (a) 1 Gly, (b) 2 Gly, (c) 3 Gly, (d) 4 Gly, (e) 5 Gly, kanye (f) 6 Gly.
Amandla wesikhala se-elekthronikhi yipharamitha eqakathekileko ekufuze iqalwe lokha nakufundwa ukusabela kwanoma ngiyiphi into ye-elekthronikhi. Ngombana ihlathulula ukuziphatha kwama-elektroni lokha izinto nazitjhugululwa ngaphandle. Ngalokho-ke, kuyatlhogeka ukulinganisa amandla wesikhala se-elekthronikhi se-HOMO/LUMO kizo zoke izakhiwo ezifundwako. Ithebula 2 litjengisa amatjhuguluko emandleni we-HOMO/LUMO we-3PVA-(C10)2Na Alg kanye ne-Term 1Na Alg − 3PVA- Mid 1Na Alg ngebanga lokungezelelwa kwe-glycerol. Ngokuya kwe-ref47, inani le-Eg le-3PVA-(C10)2Na Alg lingu-0.2908 eV, kuthi inani le-Eg lesakhiwo esitjengisa amathuba wokuthintana kwesibili (okutjho, iThemu 1Na Alg − 3PVA- Mid 1Na Alg) lingu-0.5706 eV.
Kodwana, kwatholakala bona ukungezelelwa kwe-glycerol kwabangela ukutjhuguluka okuncani kwenani le-Eg le-3PVA-(C10)2Na Alg. Lokha i-3PVA-(C10)2NaAlg nayihlangana namayunithi we-1, 2, 3, 4 kanye ne-5 we-glycerol, amanani wayo we-Eg aba yi-0.302, 0.299, 0.308, 0.289 kanye ne-0.281 eV, ngokulandelana. Kodwana, kunokuzwisisa okuqakathekileko kobana ngemva kokufaka amayunithi we-glycerol ama-3, inani le-Eg laba lincani kunaleyo ye-3PVA-(C10)2Na Alg. Imodeli emele ukusebenzisana kwe-3PVA-(C10)2Na Alg namayunithi amahlanu we-glycerol yimodeli yokusebenzisana engenzeka khulu. Lokhu kutjho bona njengombana inani lamayunithi we-glycerol likhula, amathuba wokuthintana nawo ayanda.
Khatheso, ngethuba lesibili lokuthintana, amandla we-HOMO/LUMO wamamolekhyuli wemodeli ajamele iThemu 1Na Alg − 3PVA –Mid 1Na Alg- 1Gly, Ithemu 1Na Alg − 3PVA –Mid 1Na Alg- 2Gly, Ithemu 1Na Alg − 3VA – PVA – 3PVA – 3PVA Algly, iThemu 1Na Algly I-Alg − 3PVA –Mid 1Na Alg- 4Gly, Term 1Na Alg − 3PVA –Mid 1Na Alg- 5Gly kanye ne-Term 1Na Alg − 3PVA –Mid 1Na Alg- 6Gly ziba yi-1.343, 1.34 7, 0.976, 0.607, 0.648, 6.48, e. ngokulandelana. Ithebula 2 litjengisa amandla wesikhala se-HOMO/LUMO esibalwe kizo zoke izakhiwo. Ngaphezu kwalokho, ukuziphatha okufanako kwamathuba wokuthintana wesiqhema sokuthoma kuyaphindwa lapha.
Ithiyori yebhendi kufiziksi yesimo esiqinileko ithi njengombana isikhala sebhendi sezinto ze-electrode sincipha, ukudlulisa kwe-elekthronikhi kwezinto kuyakhuphuka. Ukusebenzisa i-doping yindlela ejayelekileko yokwehlisa isikhala se-band yezinto ze-sodium-ion cathode. U-Jiang nabanye. wasebenzisa ukufaka i-Cu ukwenza ngcono ukudluliswa kwe-elekthronikhi kwe-β-NaMnO2. Ngokusebenzisa ukubalwa kwe-DFT, bathola bona ukufaka igezi kwehlisa isikhala sebhande lezinto ukusuka ku-0.7 eV ukuya ku-0.3 eV. Lokhu kutjengisa bona ukufakwa kwe-Cu kuthuthukisa ukudluliswa kwe-elekthronikhi kwe-β-NaMnO2.
I-MESP ihlathululwa njengamandla wokuthintana hlangana nokusabalaliswa kwetjhaji yamamolekhyuli netjhaji elilodwa elihle. I-MESP ithathwa njengethulusi elisebenzako lokuzwisisa nokuhlathulula ubujamo bamakhemikhali nokusabela. I-MESP ingasetjenziselwa ukuzwisisa iindlela zokuthintana hlangana nezinto ezine-polymeric. I-MESP ihlathulula ukusabalala kwetjhaji ngaphakathi kwekhompawundi efundwako. Ngaphezu kwalokho, i-MESP inikela ilwazi ngeendawo ezisebenzako ezintweni ezifundwako32. Umfanekiso 3 utjengisa amaplothi we-MESP we-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-Algly 3PVA-(C10) 2Na Alg − 5Gly ebikezelwe ku-B3LYP/6-311G(d, p) ezingeni lethiyori.
Amakhontu we-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 (f) 5 Gly.
Khatheso, umfanekiso 4 utjengisa imiphumela ebalwe ye-MESP ye-Term 1Na Alg- 3PVA – Mid 1Na Alg, 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, Ithemu 1Na Alg-3PVA – Phakathi 1Na Alg − 4Gly, Ithemu 1Na Alg- 3PVA – Phakathi 1Na Alg- 5gly kanye neThemu 1Na Alg-3PVA – Phakathi 1Na Alg − 6Gly, ngokulandelana. I-MESP ebalwe imelelwa njengokuziphatha kwekhonta. Imigqa yekhonthayi imelelwa mibala ehlukileko. Umbala ngamunye umele inani elihlukileko le-elekthronikhi. Umbala obomvu utjengisa iindawo ezine-elekthronikhi khulu nofana eziphendulako. Khatheso, umbala ophuzi umele amasayithi angathathi hlangothi 49, 50, 51 esakhiweni. Imiphumela ye-MESP itjengise bona ukusabela kwe-3PVA-(C10)2Na Alg kwanda ngokukhula kombala obomvu eduze namamodeli afundwako. Khatheso, ukuqina kombala obomvu emephini ye-MESP ye-Term 1Na Alg-3PVA – Mid 1Na Alg model molecule yehla ngebanga lokuthintana nokuqukethwe kwe-glycerol okuhlukileko. Ukutjhuguluka kokusabalala kombala obomvu eduze kwesakhiwo esiphakanyisiweko kutjengisa ukusabela, lokha ukwanda kwamandla kuqinisekisa ukwanda kwe-elekthronikhi ye-3PVA-(C10)2Na Alg model molecule ngebanga lokwanda kokuqukethwe kwe-glycerol.
I-B3LYP/6-311 g(d, p) ibalwe i-MESP Ithemu ye-1Na Alg-3PVA-Mid 1Na Alg esebenzisana (a) 1 Gly, (b) 2 Gly, (c) 3 Gly, (d) 4 Gly, (e) 5 Gly, kanye (f) 6 Gly.
Zoke izakhiwo eziphakanyisiweko zinemikhawulo yazo yokutjhisa efana ne-enthalpy, i-entropy, umthamo wokutjhisa, amandla wamahhala kanye nokutjhisa kokwakheka okubalwe emazingeni womtjhiso ahlukileko ukusuka ku-200 K ukuya ku-500 K. Ukuhlathulula ukuziphatha kwamasistimu abonakalako, ngaphezu kokufunda ukuziphatha kwawo kwe-elekthronikhi, kuyatlhogeka nokufunda ukuziphatha kwawo okutjhisako njengomsebenzi wokuthintana kwawo nomunye nomunye kubalwa kusetjenziswa iimbalo ezinikelwe kuThebuli 1. Ukufundwa kwamapharamitha womtjhiso kuthathwa njengesitjengiso esiqakathekileko sokuphendula nokuzinza kwamahlelo anjalo emazingeni womtjhiso ahlukileko.
Malungana ne-enthalpy ye-PVA trimer, ithoma ngokusabelana ne-NaAlg dimer, bese kuthi nge-OH group enamathele ku-carbon atom #10, bese ekugcineni nge-glycerol. I-enthalpy silinganiso samandla erherhweni lokutjhisa. I-enthalpy ilingana nokutjhisa okupheleleko erherhweni, okulingana namandla wangaphakathi werherho kanye nomkhiqizo womthamo nomfutho wayo. Ngamanye amagama, i-enthalpy itjengisa bona kungakanani ukutjhisa nomsebenzi okufakwako nofana okususwako entweni52.
Umfanekiso 5 utjengisa amatjhuguluko we-enthalpy ngesikhathi sokusabela kwe-3PVA-(C10)2Na Alg enamazinga ahlukileko we-glycerol. Iinfinyezo A0, A1, A2, A3, A4, kanye no-A5 zijamele amamolekhyuli wemodeli 3PVA-(C10)2Na Alg, 3PVA-(C10)2Na Alg − 1 Gly, 3PVA-(C10)2Na Alg − 2Gly, 3PVA-(C10)2Na −3Gly, 3PVA-(C10)2Na Alg − 4Gly, kanye ne-3PVA-(C10)2Na Alg − 5Gly, ngokulandelana. Umfanekiso 5a utjengisa bona i-enthalpy ikhuphuka ngokukhula kwamazinga womtjhiso kanye nokuqukethwe kwe-glycerol. I-enthalpy yesakhiwo esimele i-3PVA-(C10)2NaAlg − 5Gly (okutjho, A5) ku-200 K ngu-27.966 cal/mol, kuthi i-enthalpy yesakhiwo esimele i-3PVA- 2NaAlg ku-200 K ngu-13.490 cal/mol. Ekugcineni, njengoba i-enthalpy ilungile, ukusabela lokhu ku-endothermic.
I-entropy ihlathululwa njengesilinganiso samandla angatholakaliko erherhweni elivaliweko le-thermodynamic begodu kanengi ithathwa njengesilinganiso sokuphazamiseka kwerherho. Umfanekiso 5b utjengisa ukutjhuguluka kwe-entropy ye-3PVA-(C10)2NaAlg ngokutjhisa nokuthi isebenzisana njani namayunithi we-glycerol ahlukileko. Igrafu itjengisa bona i-entropy itjhuguluka ngokulandelana njengombana izinga lokutjhisa likhuphuka ukusuka ku-200 K ukuya ku-500 K. Umfanekiso 5b utjengisa ngokukhanyako bona i-entropy yemodeli ye-3PVA-(C10)2Na Alg ithambekele ku-200 cal/K/mol ku-200 K ngombana imodeli ye-3PVA-(C10)2Na Alg itjengisa ukuhlukana okuncani. Njengoba amazinga womtjhiso akhula, imodeli ye-3PVA-(C10)2Na Alg iyaphazamiseka begodu ihlathulula ukwanda kwe-entropy ngokunyuka kwamazinga womtjhiso. Ngaphezu kwalokho, kuyacaca bona isakhiwo se-3PVA-C10 2Na Alg- 5 Gly sinenani eliphezulu le-entropy.
Ukuziphatha okufanako kubonakala kuMfanekiso 5c, otjengisa ukutjhuguluka kwamandla womtjhiso ngokutjhisa. Umthamo wokutjhisa linani lokutjhisa elitlhogekako ukutjhugulula izinga lokutjhisa lenani elithileko lento nge-1 °C47. Umfanekiso 5c utjengisa amatjhuguluko emandleni womtjhiso we-molecule yemodeli 3PVA-(C10)2NaAlg ngebanga lokusebenzisana namayunithi we-glycerol ayi-1, 2, 3, 4, kanye ne-5. Umfanekiso utjengisa bona amandla womtjhiso wemodeli ye-3PVA-(C10)2NaAlg akhula ngokulandelana ngokutjhisa. Ukwanda okubonwako kwamandla womtjhiso ngokunyuka kwamazinga womtjhiso kubangelwa kukudlidliza kwe-phonon. Ukungezelela, kunobufakazi bokuthi ukwandisa okuqukethwe kwe-glycerol kurholela ekukhuphukeni kwamandla womtjhiso wemodeli ye-3PVA-(C10)2NaAlg. Ukudlula lapho, isakhiwo sitjengisa bona i-3PVA-(C10)2NaAlg−5Gly inenani eliphezulu lokutjhisa nayiqathaniswa nezinye izakhiwo.
Amanye amapharamitha afana namandla wamahhala kanye nokutjhisa kokugcina kokwakheka kwabalelwa izakhiwo ezifundwako begodu zitjengiswe kuMfanekiso 5d no-e, ngokulandelana. Umtjhiso wokugcina wokwakheka mtjhiso okhutjhwako nofana omunywako ngesikhathi sokwakheka kwento ehlanzekileko ukusuka eentweni ezibunjwa ngaphasi komfutho ongaguqukiko. Amandla wamahhala angachazwa njengepahla efana namandla, okutjho bona, inani lawo liya ngobunengi bezinto ezisesigabeni ngasinye se-thermodynamic. Amandla wamahhala nokutjhisa kokwakheka kwe-3PVA-(C10)2NaAlg−5Gly bekuphasi khulu begodu bekungu-1318.338 kanye no--1628.154 kcal/mol, ngokulandelana. Ngokuphikisako, isakhiwo esijamele i-3PVA-(C10)2NaAlg sinamandla aphezulu wamahhala kanye nokutjhisa kokwakheka kwamanani we--690.340 no--830.673 kcal/mol, ngokulandelana, nayiqathaniswa nezinye izakhiwo. Njengombana kutjengisiwe emfanekisweni 5, izakhiwo ezihlukahlukeneko zokutjhisa ziyatjhuguluka ngebanga lokusebenzisana ne-glycerol. Amandla wamahhala we-Gibbs angakalungi, okutjengisa bona isakhiwo esiphakanyisiweko sizinzile.
I-PM6 yabala amapharamitha womtjhiso we-3PVA- (C10) 2Na Alg (imodeli A0), 3PVA- (C10) 2Na Alg − 1 Gly (imodeli A1), 3PVA- (C10) 2Na Alg − 2 Gly (imodeli A2), 3PVA- (C10) 2Gly (imodeli A2), 3PVA-(C10) Gly-Gly 333 (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 wokutjhisa, (d) amandla wamahhala, kanye (e) nokutjhisa kokwakheka.
Ngakelinye ihlangothi, indlela yesibili yokuthintana hlangana ne-PVA trimer ne-dimeric NaAlg yenzeka emaqenjini we-OH we-terminal nephakathi esakhiweni se-PVA trimer. Njengesiqhema sokuthoma, amapharamitha womtjhiso abalwa kusetjenziswa izinga elifanako lethiyori. Umfanekiso 6a-e utjengisa ukutjhuguluka kwe-enthalpy, i-entropy, umthamo wokutjhisa, amandla wamahhala begodu, ekugcineni, ukutjhisa kokwakheka. Iinthombe 6a-c zitjengisa bona i-enthalpy, i-entropy kanye nomthamo wokutjhisa we-Term 1 NaAlg-3PVA-Mid 1 NaAlg itjengisa ukuziphatha okufanako nesiqhema sokuthoma lokha nayisebenzisana namayunithi we-1, 2, 3, 4, 5 kanye ne-6 we-glycerol. Ngaphezu kwalokho, amanani wawo akhula kancanikancani ngokukhula kwamazinga womtjhiso. Ukungezelela, kumodeli ehlongozwayo ye-Term 1 Na Alg − 3PVA-Mid 1 Na Alg, i-enthalpy, i-entropy kanye namazinga wokutjhisa akhula ngokukhula kwe-glycerol. Iinfinyezo ezithi B0, B1, B2, B3, B4, B5 kanye ne-B6 zijamele izakhiwo ezilandelako: 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 − 2 Alg, Ithemu 1 Na Alg-2 3PVA- Mid 1 Na Alg − 3gly, Term 1 Na Alg- 3PVA- Mid 1 Na Alg − 4 Gly, Term 1 Na Alg- 3PVA- Mid 1 Na Alg − 5 Gly kanye neThem 1 Na Alg- 3PVA- Mid 1 Na Alg − 6 Gly. Njengombana kutjengisiwe ku-Fig. 6a–c, kuyacaca bona amanani we-enthalpy, i-entropy kanye nekghono lokutjhisa ayanda njengombana inani lamayunithi we-glycerol likhuphuka ukusuka ku-1 ukuya ku-6.
I-PM6 yabala amapharamitha womtjhiso we-Term 1 Na Alg- 3PVA- Mid 1 Na Alg (imodeli B0), i-Term 1 Na Alg- 3PVA- Mid 1 Na Alg – 1 Gly (imodeli B1), i-Term 1 Na Alg- 3PVA- Mid 1 Na Alg – 2 Gly (imodeli B1-2 Alg-Na Alg-13), I-Na Alg – 3 Gly (imodeli B3), iThemu 1 Na Alg- 3PVA- Mid 1 Na Alg – 4 Gly (imodeli B4), Ithemu 1 Na Alg- 3PVA- Mid 1 Na Alg – 5 Gly (imodeli B5), kanye neThemu 1 Na Alg- 3PVA- Mid 1 Na Alg – 6 Gly (imodeli B5), kufaka hlangana enpy i-entropy, (c) umthamo wokutjhisa, (d) amandla wamahhala, kanye (e) nokutjhisa kokwakheka.
Ukungezelela, isakhiwo esijamele i-Term 1 Na Alg- 3PVA- Mid 1 Na Alg- 6 Gly sinamanani aphezulu we-enthalpy, i-entropy kanye ne-heat capacity nayiqathaniswa nezinye izakhiwo. Hlangana nazo, amanani wazo akhuphuke ukusuka ku-16.703 cal/mol, 257.990 cal/mol/K kanye ne-131.323 kcal/mol ku-Term 1 Na Alg − 3PVA- Mid 1 Na Alg ukuya ku-33.223 cal/mol, 420.038 cal/mol/mol/mol ngeThemu 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly, ngokulandelana.
Kodwana, iimfanekiso 6d no-e zitjengisa ukuthembela emazingeni womtjhiso wamandla wamahhala kanye nokutjhisa kokugcina kokwakheka (HF). I-HF ingachazwa njengokutjhuguluka kwe-enthalpy okwenzekako lokha i-mole eyodwa yento nayibunjwa ngezakhi zayo ngaphasi kwemibandela yemvelo nejwayelekileko. Kuyabonakala emfanekisweni bona amandla wamahhala kanye nokutjhisa kokugcina kokwakheka kwazo zoke izakhiwo ezifundwako zitjengisa ukuthembela okuqondileko emazingeni womtjhiso, okutjho bona, zikhula kancanikancani begodu ngokulandelana ngokukhuphuka kwezinga lokutjhisa. Ukungezelela, isibalo siqinisekise nokuthi isakhiwo esijamele iThemu 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly sinamandla aphasi khulu wamahhala kanye ne-HF ephasi khulu. Bobabili amapharamitha wehle ukusuka ku--758.337 ukuya ku-899.741 K cal/mol ngethemu 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly ukuya ku--1,476.591 kanye no--1,828.523 K cal/mol. Kuyabonakala emiphumeleni bona i-HF yehla ngokukhula kwamayunithi we-glycerol. Lokhu kutjho bona ngebanga lokwanda kwamaqembu asebenzako, ukusabela nakho kuyakhuphuka begodu ngalokho kutlhogeka amandla amancani ukwenza ukusabela. Lokhu kuqinisekisa bona i-PVA/NaAlg eplastiki ingasetjenziswa emabhetri ngebanga lokusebenza kwayo okukhulu.
Ngokuvamileko, imiphumela yamazinga womtjhiso ihlukaniswe yaba mihlobo emibili: imiphumela yamazinga womtjhiso aphasi nemiphumela yamazinga womtjhiso aphezulu. Imithelela yamazinga womtjhiso aphasi izwakala khulu emazweni asema-latitude aphezulu, njenge-Greenland, Canada, ne-Russia. Ebusika, amazinga womtjhiso womoya wangaphandle eendaweni lezi angaphasi khulu kwama-degree Celsius. Isikhathi sokuphila nokusebenza kwamabhetri we-lithium-ion kungathinteka ngamazinga womtjhiso aphasi, khulukhulu lawo asetjenziswa eenkoloyini ezisebenzisa i-plug-in, ezisebenzisa igezi, kanye neenkoloyi ezisebenzisa igezi. Ukukhamba emkhathini kungenye indawo ebandako edinga amabhetri we-lithium-ion. Ukwenza isibonelo, amazinga womtjhiso e-Mars angehlela ku--120 degrees Celsius, okubeka isithiyo esikhulu ekusetjenzisweni kwamabhetri we-lithium-ion emkhunjini. Amazinga womtjhiso aphasi wokusebenza angadosela ekwehleni kwezinga lokudluliswa kwetjhaji kanye nomsebenzi wokuphendula kwamakhemikhali wamabhetri we-lithium-ion, okurholela ekwehleni kwezinga lokusabalala kwama-ion we-lithium ngaphakathi kwe-electrode kanye nokudluliswa kwe-ayoni ku-electrolyte. Ukuwohloka lokhu kuphumela ekwehliseni umthamo wamandla namandla, begodu kesinye isikhathi kuphumela ekunciphiseni ukusebenza53.
Umphumela wokutjhisa okuphezulu wenzeka eendaweni ezinengi zokusebenzisa, kufaka hlangana zombili iindawo zokutjhisa eziphezulu neziphasi, ngesikhathi umphumela wokutjhisa okuphasi ulinganiselwe khulu eendaweni zokusebenzisa ezitjhisako eziphasi. Umphumela wezinga lokutjhisa eliphasi unqunywa khulu lizinga lokutjhisa eliseduze, kuthi umphumela wezinga lokutjhisa eliphezulu uvamise ukuhlotjaniswa ngokunembileko emazingeni womtjhiso aphezulu ngaphakathi kwebhetri ye-lithium-ion ngesikhathi sokusebenza.
Amabhetri we-lithium-ion akhiqiza ukutjhisa ngaphasi kweemeko eziphezulu zamanje (okufaka hlangana ukutjhaja msinyana nokukhipha msinyana), okwenza bona amazinga womtjhiso wangaphakathi akhuphuke. Ukuvezwa emazingeni womtjhiso aphezulu kungabangela ukuwohloka kokusebenza kwebhetri, okufaka hlangana ukulahlekelwa mthamo namandla. Ngokuvamileko, ukulahlekelwa kwe-lithium nokubuyiswa kwezinto ezisebenzako emazingeni womtjhiso aphezulu kurholela ekulahlekelweni kwamandla, begodu ukulahlekelwa kwamandla kungenxa yokwanda kokujamelana kwangaphakathi. Nangabe izinga lokutjhisa lingasalawuleki, kubaleka ukutjhisa, okuthi kwezinye izehlakalo kungaholela ekuvutheni okuzenzakalelayo nofana ukuqhuma.
Iimbalo ze-QSAR yindlela yokwenza imodeli yekhomphyutha nofana yeembalo esetjenziselwa ukukhomba ubudlelwano hlangana nomsebenzi wezinto eziphilako kanye nezakhiwo zamakhompawundi. Woke amamolekhyuli aklanyelwe ngcono begodu ezinye izakhiwo ze-QSAR zabalwa ezingeni le-PM6. Ithebula 3 libala ezinye zeenhlathululo ze-QSAR ezibalwe. Iimbonelo zeenhlathululo ezinjalo yi-charge, i-TDM, amandla woke (E), i-ionization potential (IP), i-Log P, kanye ne-polarizability (qala ithebula 1 malungana namafomula wokuthola i-IP ne-Log P).
Imiphumela yokubala itjengisa bona umthwalo opheleleko wazo zoke izakhiwo ezifundwako ngu-zero ngombana zisebujameni obuphasi. Ukuze kube nokuthintana kokuthoma, i-TDM ye-glycerol beyiyi-2.788 Debye kanye ne-6.840 Debye ye-3PVA-(C10) 2Na Alg, ngesikhathi amanani we-TDM akhuphukela ku-17.990 Debye, 8.848 Debye, 5.874 Debye, 7.658 Debye kanye ne-Debye 7.777. I-3PVA-(C10) 2Na Alg isebenzisane namayunithi ayi-1, 2, 3, 4 kanye nama-5 we-glycerol, ngokulandelana. Inani le-TDM eliphezulu, ukuphendula kwalo nebhoduluko kuphezulu.
Amandla woke (E) nawo abalwa, begodu amanani we-E we-glycerol ne-3PVA-(C10)2 NaAlg atholakala angu--141.833 eV no-200092.503 eV, ngokulandelana. Khatheso, izakhiwo ezijamele i-3PVA-(C10)2 NaAlg zisebenzisana namayunithi we-glycerol ayi-1, 2, 3, 4 kanye ne-5; I-E iba ngu-996.837, -1108.440, -1238.740, -1372.075 kanye no-1548.031 eV, ngokulandelana. Ukukhuphula i-glycerol kurholela ekwehleni kwamandla woke begodu lokho kuholela ekukhuphukeni kokusabela. Ngokuya ngokubalwa kwamandla woke, kwaphethwa ngokuthi i-molecule yemodeli, okuyi-3PVA-2Na Alg-5 Gly, iyaphendula khulu kunamanye ama-molecule wemodeli. Isimanga lesi sihlobene nesakhiwo sabo. I-3PVA-(C10)2NaAlg inamaqembu amabili we--COONa kwaphela, lokha ezinye izakhiwo ziqukethe amaqembu amabili we-COONa kodwana zithwele amaqembu we-OH amanengi, okutjho bona ukuphendula kwazo ebhodulukweni kukhuphuka.
Ngaphezu kwalokho, amandla we-ionization (IE) wazo zoke izakhiwo ayaqalwa esifundweni lesi. Amandla we-ionization yipharamitha eqakathekileko yokulinganisa ukusabela kwemodeli efundwako. Amandla atlhogekako ukuthutha i-elektroni ukusuka endaweni eyodwa ye-molecule ukuya ekungapheliko abizwa ngokuthi amandla we-ionization. Ijamele izinga loku-ayoni (okutjho ukusabela) kwe-molecule. Nayikuthi amandla we-ionization aphezulu, ukuphendula kuyaphasi. Imiphumela ye-IE ye-3PVA-(C10)2NaAlg esebenzisana namayunithi we-1, 2, 3, 4 kanye ne-5 we-glycerol bekungu--9.256, -9.393, -9.393, -9.248 kanye no-9.323 eV, ngokulandelana, kuthi ama-IE we-glycerol ne-PVA-(C10)15-Alg kanye no-9.341 eV, ngokulandelana. Njengombana ukungezelelwa kwe-glycerol kwabangela ukwehla kwenani le-IP, ukusabela kwamamolekhyuli kwanda, okuthuthukisa ukusetjenziswa kwe-PVA/NaAlg/glycerol model molecule kumadivayisi we-electrochemical.
Ihlathululo yesihlanu kuThebuli 3 yi-Log P, okuyi-logarithm ye-partition coefficient begodu isetjenziselwa ukuhlathulula bona isakhiwo esifundwako sithanda amanzi nofana asithandi amanzi. Inani elingakalungi le-Log P litjengisa i-molecule ethanda amanzi, okutjho bona incibilika lula emanzini begodu incibilika kumbi eentweni eziphilako. Inani elihle litjengisa ikambiso ephikisanako.
Ngokuya ngemiphumela etholakeleko, kungaphethwa ngokuthi zoke izakhiwo zithanda amanzi, ngombana amanani wazo we-Log P (3PVA-(C10)2Na Alg − 1Gly, 3PVA-(C10)2Na Alg − 2Gly, 3PVA-(C10)2Na Alg − 3Gly, PVA-(C10)2Na Alg −3Gly I-4Gly kanye ne-3PVA-(C10)2Na Alg − 5Gly) yi--3.537, -5.261, -6.342, -7.423 kanye ne-8.504, ngokulandelana, kuthi inani le-Log P le-glycerol lingu-1.081 kwaphela begodu i-3PVA-(C10)2Na lingu-Alg -1030 kwaphela. Lokhu kutjho bona izakhiwo zesakhiwo esifundwako zizokutjhuguluka njengombana amamolekhyuli wamanzi afakwa esakhiweni saso.
Ekugcineni, ukuhlukana kwazo zoke izakhiwo nakho kubalwa ezingeni le-PM6 kusetjenziswa indlela ye-semi-empirical. Bekutjhejwe ngaphambilini bona ukuhlukaniswa kwezinto ezinengi kuya ngezinto ezihlukahlukeneko. Into eqakatheke khulu mthamo wesakhiwo esifundwako. Kizo zoke izakhiwo ezibandakanya umhlobo wokuthoma wokuthintana hlangana ne-3PVA ne-2NaAlg (ukusebenzisana kwenzeka nge-athomu yekhabhoni enomboro 10), ukutjhuguluka kwe-polarizability kuthuthukiswa ngokungezelelwa kwe-glycerol. Ukuphambuka kukhuphuka ukusuka ku-29.690 Å ukuya ku-35.076, 40.665, 45.177, 50.239 kanye no-54.638 Å ngebanga lokusebenzisana namayunithi we-1, 2, 3, 4 kanye ne-5 we-glycerol. Ngalokho, kwatholakala bona imodeli ye-molecule ene-polarizability ephezulu khulu yi-3PVA-(C10)2NaAlg−5Gly, kuthi imodeli ye-molecule ene-polarizability ephasi khulu yi-3PVA-(C10)2NaAlg, okungu-29.690 Å.
Ukuhlolwa kweenhlathululo ze-QSAR kuveze bona isakhiwo esijamele i-3PVA-(C10)2NaAlg − 5Gly siphendula khulu ekusebenzisaneni kokuthoma okuphakanyisiweko.
Ngendlela yesibili yokusebenzisana hlangana ne-PVA trimer ne-NaAlg dimer, imiphumela itjengisa bona iindleko zazo zifana nalezo eziphakanyiswe esigabeni esidlulileko sokusebenzisana kokuthoma. Zoke izakhiwo azikho ukutjhaja kwe-elekthronikhi, okutjho bona zoke zisebujameni obuphasi.
Njengombana kutjengiswe kuThebuli 4, amanani we-TDM (abalwe ngezinga le-PM6) we-Term 1 Na Alg − 3PVA-Mid 1 Na Alg akhuphuke ukusuka ku-11.581 Debye ukuya ku-15.756, 19.720, 21.756, 22.732, 15.507, 15.507, kanye ne-Alg −5151, kanye ne-Na Alg − I-3PVA-Mid 1 Na Alg yaphendula nge-1, 2, 3, 4, 5, kanye namayunithi we-glycerol ayi-6. Kodwana, amandla woke ayancipha ngokukhula kwenani lamayunithi we-glycerol, begodu lokha i-Term 1 Na Alg − 3PVA- Mid 1 Na Alg nayisebenzisana nenani elithileko lamayunithi we-glycerol (1 ukuya ku-6), amandla woke angu-− 996.985, − 1129.013, − 1267, −127, −177. 1418.964, kanye no-− 1637.432 eV, ngokulandelana.
Ngokwethuba lokusebenzisana kwesibili, i-IP, i-Log P kanye nokuhlukana nakho kubalwa ezingeni le-PM6 lethiyori. Ngalokho-ke, bacabangela iinhlathululo ezintathu ezinamandla khulu zokusabela kwamamolekhyuli. Ezakhiweni ezijamele i-End 1 Na Alg-3PVA-Mid 1 Na Alg esebenzisana namayunithi we-1, 2, 3, 4, 5 kanye ne-6 ye-glycerol, i-IP ikhuphuka ukusuka ku-−9.385 eV ukuya ku-−8.946, −8.848, −8.430, −9.537, −7.997, −8.999 kanye ne-eV. Kodwana, inani le-Log P elibalwe beliphasi ngebanga lokuplastikisa kwe-End 1 Na Alg-3PVA-Mid 1 Na Alg nge-glycerol. Njengombana i-glycerol ikhuphuka ukusuka ku-1 ukuya ku-6, amanani wayo aba ngu-5.334, -6.415, -7.496, -9.096, -9.861 kanye no-10.53 kuno--3.643. Ekugcineni, idatha ye-polarizability itjengise bona ukwandisa okuqukethwe kwe-glycerol kuphumele ekukhuphukeni kwe-polarizability ye-Term 1 Na Alg- 3PVA- Mid 1 Na Alg. I-polarizability ye-model molecule Term 1 Na Alg- 3PVA- Mid 1 Na Alg ikhuphuke ukusuka ku-31.703 Å ukuya ku-63.198 Å ngemva kokuthintana namayunithi we-glycerol ayi-6. Kuqakathekile ukutjheja bona ukwandisa inani lamayunithi we-glycerol ekuhlanganeni kwesibili kwenziwa ukuqinisekisa bona nanyana kunenani elikhulu lama-athomu nesakhiwo esiyinkimbinkimbi, ukusebenza kusathuthukiswa ngokunyuka kokuqukethwe kwe-glycerol. Ngalokho, kungatjhiwo bona imodeli ye-PVA/Na Alg/glycerin ekhona ingathatha indawo yamabhetri we-lithium-ion, kodwana kutlhogeka irhubhululo nentuthuko enengi.
Ukuhlathulula amandla wokubophelela wephasi ne-adsorbate nokuhlola ukusebenzisana okuhlukileko hlangana namasistimu kutlhoga ilwazi lomhlobo wokubopha okukhona hlangana nanyana ngimaphi ama-athomu amabili, ubudisi bokuthintana hlangana namamolekhyuli nangaphakathi kwamamolekhyuli, kanye nokusabalala kwe-elekthronikhi yephasi ne-adsorbent. Ukuminyana kwama-elekthronikhi endaweni eqakathekileko yokubopha (BCP) hlangana nama-athomu asebenzisanako kuqakathekile ekuhloleni amandla wokubopha ekuhlaziyweni kwe-QTAIM. Nayikuthi ukuminyana kwe-elekthronikhi kuphezulu, ukusebenzisana kwe-covalent kuyazinza begodu, ngokuvamileko, ukuminyana kwe-elekthronikhi kuphezulu eendaweni eziqakathekileko. Ngaphezu kwalokho, nangabe kokubili ukuminyana kwamandla we-elekthronikhi (H(r)) kanye nokuminyana kwe-Laplace charge (∇2ρ(r)) kungaphasi kuka-0, lokhu kutjengisa ubukhona bokusebenzisana kwe-covalent (okujayelekileko). Ngakelinye ihlangothi, lokha i-∇2ρ(r) ne-H(r) zingaphezu kuka-0.54, kutjengisa ubukhona bokusebenzisana okungasikho kwe-covalent (igobolondo elivaliweko) okufana namabhondi we-hydrogen abuthakathaka, amandla we-van der Waals kanye nokusebenzisana kwe-elekthrostatic. Ukuhlaziywa kwe-QTAIM kuveze ubujamo bokusebenzisana okungasikho kwe-covalent ezakhiweni ezifundwako njengombana kutjengisiwe emifanekisweni 7 no-8. Ngokuya ngokuhlaziywa, amamolekhyuli wemodeli ajamele i-3PVA − 2Na Alg kanye ne-Term 1 Na Alg − 3PVA –Mid 1 Na Alg atjengisa ukuzinza okuphezulu kunamamolekhyuli asebenzisana ngokuhlukileko namayunithi we-g. Lokhu kungenxa yokuthi inani lokusebenzisana okungasikho kwe-covalent okuvame khulu esakhiweni se-alginate okufana nokusebenzisana kwe-electrostatic kanye namabhondi we-hydrogen kwenza bona i-alginate iqinise ama-composites. Ukudlula lapho, imiphumela yethu itjengisa ukuqakatheka kokusebenzisana okungasikho kwe-covalent hlangana ne-3PVA − 2Na Alg kanye ne-Term 1 Na Alg − 3PVA –Mid 1 Na Alg amamolekhuli wemodeli kanye ne-glycine, okutjengisa bona i-glycine idlala indima eqakathekileko ekuguquleni ubujamo be-elekthronikhi boke bezinto ezihlanganisiweko.
Ukuhlaziywa kwe-QTAIM kwe-molecule yemodeli 3PVA − 2NaAlg esebenzisana (a) 0 Gly, (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, kanye (f) 5Gly.