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Ma muli o ka nui o ke kumuwaiwai sodium, ʻo nā pila sodium-ion (NIB) ke kū nei i kahi hopena ʻē aʻe e hoʻohiki ai no ka mālama ʻana i ka ikehu electrochemical. I kēia manawa, ʻo ke keakea nui i ka hoʻomohala ʻana o ka ʻenehana NIB ʻo ia ka nele o nā mea electrode e hiki ke mālama/hoʻokuʻu i nā ion sodium no ka manawa lōʻihi. No laila, ʻo ka pahuhopu o kēia haʻawina, ʻo ia ke noiʻi i ka hopena o ka hoʻohui ʻana o ka glycerol ma ka polyvinyl alcohol (PVA) a me nā hui sodium alginate (NaAlg) ma ke ʻano he mau mea electrode NIB. Ke nānā nei kēia haʻawina i nā wehewehe pilina hana-hana uila, thermal, a me ka quantitative (QSAR) o nā electrolytes polymer e pili ana i ka PVA, sodium alginate, a me nā hui glycerol. Ua noiʻi ʻia kēia mau waiwai me ka hoʻohana ʻana i nā ʻano semi-empirical a me ke kumumanaʻo hana density (DFT). ʻOiai ua hōʻike ka loiloi kūkulu i nā kikoʻī o nā pilina ma waena o PVA/alginate a me glycerol, ua noiʻi ʻia ka ikehu band gap (Eg). Hōʻike nā hopena i ka hoʻohui ʻana o ka glycerol e hopena i ka emi ʻana o ka waiwai Eg i 0.2814 eV. Hōʻike ka ʻili hiki ke electrostatic molecular (MESP) i ka hoʻolaha ʻana o nā ʻāpana waiwai-electron a me nā ʻilihune-electron a me nā uku molecular i loko o ka ʻōnaehana electrolyte holoʻokoʻa. ʻO nā ʻano thermal i aʻo ʻia e pili ana i ka enthalpy (H), entropy (ΔS), ka hiki ke wela (Cp), ka ikehu manuahi Gibbs (G) a me ka wela o ka hoʻokumu ʻana. Eia kekahi, ua noiʻi ʻia kekahi mau wehewehe pilina hana-hana quantitative (QSAR) e like me ka manawa dipole holoʻokoʻa (TDM), ka ikehu holoʻokoʻa (E), ka hiki ke ionization (IP), Log P a me ka polarizability i loko o kēia haʻawina. Ua hōʻike nā hopena ua hoʻonui ʻia ʻo H, ΔS, Cp, G a me TDM me ka hoʻonui ʻana i ka mahana a me ka ʻike glycerol. I kēia manawa, ua emi ka wela o ka hoʻokumu ʻana, IP a me E, kahi i hoʻomaikaʻi ai i ka reactivity a me ka polarizability. Eia kekahi, ma ka hoʻohui ʻana i ka glycerol, ua hoʻonui ʻia ka voltage cell i 2.488 V. Hōʻike nā helu DFT a me PM6 e pili ana i nā electrolytes PVA/Na Alg glycerol-based cost-effective hiki iā lākou ke pani hapa i nā pila lithium-ion ma muli o ko lākou multifunctionality, akā pono nā hoʻomaikaʻi hou aʻe a me ka noiʻi.
ʻOiai ua hoʻohana nui ʻia nā pila lithium-ion (LIB), ke kū nei kā lākou noi i nā palena he nui ma muli o ko lākou ola pōʻaiapuni pōkole, ke kumukūʻai kiʻekiʻe, a me nā hopohopo palekana. Hiki i nā pila sodium-ion (SIB) ke lilo i koho kūpono i nā LIB ma muli o ko lākou loaʻa ākea, ke kumukūʻai haʻahaʻa, a me ka ʻawaʻawa ʻole o ka mea sodium. Ke lilo nei nā pila sodium-ion (SIB) i ʻōnaehana mālama ikehu koʻikoʻi no nā mea electrochemical1. Hilinaʻi nui nā pila sodium-ion i nā electrolytes e hoʻomaʻamaʻa i ka lawe ʻana o ka ion a hoʻoulu i ke au uila2,3. ʻO nā electrolytes wai ka mea nui i hana ʻia me nā paʻakai metala a me nā mea hoʻoheheʻe organik. Pono nā noi hana e noʻonoʻo pono i ka palekana o nā electrolytes wai, ʻoiai ke kau ʻia ka pila i ke kaumaha wela a uila paha4.
Manaʻo ʻia nā pila Sodium-ion (SIB) e pani i nā pila lithium-ion i ka wā e hiki mai ana ma muli o ko lākou mau waihona kai nui, ka ʻawaʻawa ʻole, a me ke kumukūʻai haʻahaʻa. Ua wikiwiki ka hana ʻana o nā nanomaterials i ka hoʻomohala ʻana o ka mālama ʻikepili, nā mea uila, a me nā mea optical. Ua hōʻike kahi kino nui o nā palapala i ka hoʻohana ʻana o nā nanostructures like ʻole (e laʻa, nā oxides metala, graphene, nanotubes, a me fullerenes) i nā pila sodium-ion. Ua kālele ka noiʻi i ka hoʻomohala ʻana i nā mea anode, me nā polymers, no nā pila sodium-ion ma muli o ko lākou versatility a me ke aloha i ke kaiapuni. E piʻi nui ana ka hoihoi noiʻi ma ke kahua o nā pila polymer rechargeable. ʻO nā mea electrode polymer hou me nā ʻano a me nā waiwai kū hoʻokahi e hoʻomākaukau i ke ala no nā ʻenehana mālama ikehu aloha i ke kaiapuni. ʻOiai ua ʻimi ʻia nā mea electrode polymer like ʻole no ka hoʻohana ʻana i nā pila sodium-ion, aia nō kēia kahua i kona mau pae mua o ka hoʻomohala ʻana. No nā pila sodium-ion, pono e ʻimi ʻia nā mea polymer hou aʻe me nā hoʻonohonoho ʻano like ʻole. Ma muli o ko mākou ʻike o kēia manawa e pili ana i ke ʻano mālama o nā ion sodium i loko o nā mea electrode polymer, hiki ke kuhiakau ʻia e hiki i nā hui carbonyl, nā radical free, a me nā heteroatoms i loko o ka ʻōnaehana i hoʻohui ʻia ke lawelawe ma ke ʻano he mau wahi hana no ka launa pū ʻana me nā ion sodium. No laila, he mea nui e hoʻomohala i nā polymers hou me ka nui o kēia mau wahi hana. ʻO ka electrolyte polymer Gel (GPE) kahi ʻenehana ʻē aʻe e hoʻomaikaʻi ai i ka hilinaʻi o ka pila, ka conductivity ion, ʻaʻohe leakage, ka maʻalahi kiʻekiʻe, a me ka hana maikaʻi12.
ʻO nā matrices polymer e komo pū me nā mea e like me PVA a me ka polyethylene oxide (PEO)13. Hoʻopaʻa ka polymer permeable gel (GPE) i ka electrolyte wai i loko o ka matrix polymer, kahi e hōʻemi ai i ka pilikia o ka leakage i hoʻohālikelike ʻia me nā mea hoʻokaʻawale kalepa14. He polymer biodegradable synthetic ka PVA. Loaʻa iā ia kahi permittivity kiʻekiʻe, he pipiʻi a ʻaʻohe ʻawaʻawa. Ua kaulana ka mea no kona mau waiwai hana kiʻiʻoniʻoni, ke kūpaʻa kemika a me ka hoʻopili ʻana. Loaʻa iā ia nā hui hana (OH) a me kahi density hiki ke hoʻopili ʻia kiʻekiʻe15,16,17. Ua hoʻohana ʻia ka hoʻohuihui polymer, ka hoʻohui plasticizer, ka hoʻohui composite a me nā ʻano hana polymerization in situ e hoʻomaikaʻi i ka conductivity o nā electrolytes polymer e pili ana i ka PVA e hōʻemi i ka crystallinity matrix a hoʻonui i ka flexibility chain18,19,20.
ʻO ke kāwili ʻana he ʻano hana koʻikoʻi no ka hoʻomohala ʻana i nā mea polymeric no nā noi ʻoihana. Hoʻohana pinepine ʻia nā kāwili Polymer e: (1) hoʻomaikaʻi i nā waiwai hana o nā polymers kūlohelohe i nā noi ʻoihana; (2) hoʻomaikaʻi i nā waiwai kemika, kino, a me nā mechanical o nā mea biodegradable; a (3) hoʻololi i ke koi wikiwiki e loli nei no nā mea hou i ka ʻoihana ʻōpala meaʻai. ʻAʻole like me ka copolymerization, ʻo ka kāwili polymer kahi hana haʻahaʻa ke kumu kūʻai e hoʻohana ana i nā kaʻina hana kino maʻalahi ma mua o nā kaʻina hana kemika paʻakikī e hoʻokō i nā waiwai i makemake ʻia21. No ka hana ʻana i nā homopolymers, hiki i nā polymers like ʻole ke launa pū ma o nā mana dipole-dipole, nā pilina hydrogen, a i ʻole nā ​​​​​​complexes hoʻoili-uku22,23. Hiki i nā kāwili i hana ʻia mai nā polymers kūlohelohe a me synthetic ke hoʻohui i ka biocompatibility maikaʻi me nā waiwai mechanical maikaʻi loa, e hana ana i kahi mea maikaʻi loa ma ke kumukūʻai hana haʻahaʻa24,25. No laila, ua nui ka hoihoi i ka hana ʻana i nā mea polymeric biorelevant ma ka kāwili ʻana i nā polymers synthetic a me nā polymers kūlohelohe. Hiki ke hui pū ʻia ka PVA me ka sodium alginate (NaAlg), cellulose, chitosan a me ka starch26.
ʻO ka sodium alginate kahi polymer kūlohelohe a me ka polysaccharide anionic i unuhi ʻia mai ka algae brown moana. ʻO ka sodium alginate he β-(1-4)-linked D-mannuronic acid (M) a me α-(1-4)-linked L-guluronic acid (G) i hoʻonohonoho ʻia i loko o nā ʻano homopolymeric (poly-M a me poly-G) a me nā poloka heteropolymeric (MG a i ʻole GM)27. ʻO ka nui a me ka lakio pili o nā poloka M a me G he hopena koʻikoʻi i nā waiwai kemika a me ke kino o ka alginate28,29. Hoʻohana nui ʻia a aʻo ʻia ka sodium alginate ma muli o kona biodegradability, biocompatibility, haʻahaʻa ke kumukūʻai, nā waiwai hana kiʻiʻoniʻoni maikaʻi, a me ka ʻawaʻawa ʻole. Eia nō naʻe, ʻo ka nui o nā hui hydroxyl (OH) a me carboxylate (COO) manuahi i loko o ke kaulahao alginate e hoʻolilo i ka alginate i hydrophilic loa. Eia nō naʻe, he maikaʻi ʻole nā ​​​​​​waiwai mechanical o alginate ma muli o kona brittleness a me ka paʻakikī. No laila, hiki ke hui pū ʻia ka alginate me nā mea synthetic ʻē aʻe e hoʻomaikaʻi i ka ʻike wai a me nā waiwai mechanical30,31.
Ma mua o ka hoʻolālā ʻana i nā mea electrode hou, hoʻohana pinepine ʻia nā helu DFT e loiloi i ka hiki ke hana ʻia o nā mea hou. Eia kekahi, hoʻohana nā kānaka ʻepekema i ke kumu hoʻohālike molekala e hōʻoia a wānana i nā hopena hoʻokolohua, mālama i ka manawa, hōʻemi i ka ʻōpala kemika, a wānana i ke ʻano o ka launa pū ʻana32. Ua lilo ke kumu hoʻohālike molekala i lālā ikaika a koʻikoʻi o ka ʻepekema ma nā ʻano he nui, me ka ʻepekema mea, nā nanomaterials, kemika computational, a me ka ʻike lāʻau lapaʻau33,34. Ma ka hoʻohana ʻana i nā polokalamu hoʻohālike, hiki i nā kānaka ʻepekema ke loaʻa pololei i ka ʻikepili molekala, me ka ikehu (wela o ka hoʻokumu ʻana, ka hiki ke ionization, ka ikehu hoʻāla, a me nā mea ʻē aʻe) a me ke geometry (nā kihi pilina, nā lōʻihi pilina, a me nā kihi torsion)35. Eia kekahi, hiki ke helu ʻia nā waiwai uila (uku, HOMO a me LUMO band gap energy, electron affinity), nā waiwai spectral (nā ʻano vibrational hiʻohiʻona a me nā ikaika e like me FTIR spectra), a me nā waiwai bulk (volume, diffusion, viscosity, modulus, a me nā mea ʻē aʻe)36.
Hōʻike ʻo LiNiPO4 i nā pono kūpono i ka hoʻokūkū ʻana me nā mea electrode maikaʻi o ka pākaukau lithium-ion ma muli o kona nui o ka ikehu (ka uila hana ma kahi o 5.1 V). No ka hoʻohana piha ʻana i ka pono o LiNiPO4 ma ka ʻāpana voltage kiʻekiʻe, pono e hoʻohaʻahaʻa ʻia ka uila hana no ka mea hiki i ka electrolyte voltage kiʻekiʻe i hoʻomohala ʻia i kēia manawa ke noho paʻa wale nō ma nā voltage ma lalo o 4.8 V. Ua noiʻi ʻo Zhang et al. i ka doping o nā metala hoʻololi 3d, 4d, a me 5d āpau ma kahi Ni o LiNiPO4, koho i nā ʻano doping me ka hana electrochemical maikaʻi loa, a hoʻoponopono i ka uila hana o LiNiPO4 me ka mālama ʻana i ke kūpaʻa o kāna hana electrochemical. ʻO nā voltage hana haʻahaʻa loa a lākou i loaʻa ai he 4.21, 3.76, a me 3.5037 no Ti, Nb, a me Ta-doped LiNiPO4.
No laila, ʻo ka pahuhopu o kēia haʻawina, ʻo ia ke noiʻi i ka hopena o ka glycerol ma ke ʻano he plasticizer ma nā waiwai uila, nā wehewehe QSAR a me nā waiwai thermal o ka ʻōnaehana PVA/NaAlg me ka hoʻohana ʻana i nā helu mechanical quantum no kāna noi ʻana i nā pila ion-ion rechargeable. Ua kālailai ʻia nā pilina molekala ma waena o ke kumu hoʻohālike PVA/NaAlg a me ka glycerol me ka hoʻohana ʻana i ke kumumanaʻo atomika quantum o Bader o nā molekala (QTAIM).
Ua hoʻonohonoho pono ʻia kahi kumu hoʻohālike molekala e hōʻike ana i ka launa pū ʻana o PVA me NaAlg a laila me ka glycerol me ka hoʻohana ʻana i ka DFT. Ua helu ʻia ke kumu hoʻohālike me ka hoʻohana ʻana i ka polokalamu Gaussian 0938 ma ka Spectroscopy Department, National Research Center, Cairo, Egypt. Ua hoʻonohonoho pono ʻia nā kumu hoʻohālike me ka hoʻohana ʻana i ka DFT ma ka pae B3LYP/6-311G(d, p)39,40,41,42. No ka hōʻoia ʻana i ka launa pū ʻana ma waena o nā kumu hoʻohālike i aʻo ʻia, hōʻike nā haʻawina alapine i hana ʻia ma ka pae like o ke kumumanaʻo i ke kūpaʻa o ka geometry i hoʻonohonoho pono ʻia. ʻO ka loaʻa ʻole o nā alapine maikaʻi ʻole ma waena o nā alapine i loiloi ʻia e hōʻike ana i ka ʻano i manaʻo ʻia ma ka minima maikaʻi maoli ma ka ʻili ikehu hiki. Ua helu ʻia nā ʻano kino e like me TDM, HOMO/LUMO band gap energy a me MESP ma ka pae mechanical quantum like o ke kumumanaʻo. Eia kekahi, ua helu ʻia kekahi mau palena wela e like me ka wela hope loa o ka hoʻokumu ʻana, ka ikehu manuahi, ka entropy, ka enthalpy a me ka mana wela me ka hoʻohana ʻana i nā formula i hāʻawi ʻia ma ka Papa 1. Ua hoʻokomo ʻia nā kumu hoʻohālike i aʻo ʻia i ka loiloi quantum theory of atoms in molecules (QTAIM) i mea e ʻike ai i nā pilina e hana nei ma ka ʻili o nā ʻano i aʻo ʻia. Ua hana ʻia kēia mau helu me ka hoʻohana ʻana i ke kauoha "output=wfn" ma ke code polokalamu Gaussian 09 a laila ʻike ʻia me ka hoʻohana ʻana i ke code polokalamu Avogadro43.
ʻO E ka ikehu kūloko, ʻo P ke kaomi, ʻo V ka nui, ʻo Q ka hoʻololi wela ma waena o ka ʻōnaehana a me kona wahi noho, ʻo T ka mahana, ʻo ΔH ka loli enthalpy, ʻo ΔG ka loli ikehu manuahi, ʻo ΔS ka loli entropy, ʻo a a me b nā palena haʻalulu, ʻo q ka hoʻouka atomika, a ʻo C ka nui o ka electron atomika44,45. ʻO ka hope loa, ua hoʻomaikaʻi ʻia nā ʻano like a ua helu ʻia nā palena QSAR ma ka pae PM6 me ka hoʻohana ʻana i ke code polokalamu SCIGRESS46 ma ka Spectroscopy Department o ke National Research Center ma Cairo, ʻAigupita.
Ma kā mākou hana ma mua47, ua loiloi mākou i ke kumu hoʻohālike kūpono loa e wehewehe ana i ka launa pū ʻana o ʻekolu mau ʻāpana PVA me ʻelua mau ʻāpana NaAlg, me ka glycerol e hana ana ma ke ʻano he plasticizer. E like me ka mea i ʻōlelo ʻia ma luna, aia ʻelua mau mea hiki no ka launa pū ʻana o PVA a me NaAlg. ʻO nā kumu hoʻohālike ʻelua, i kapa ʻia ʻo 3PVA-2Na Alg (ma muli o ka helu kalapona 10) a me ka Term 1Na Alg-3PVA-Mid 1Na Alg, loaʻa ka waiwai liʻiliʻi loa o ka ikehu48 i hoʻohālikelike ʻia me nā ʻano hana ʻē aʻe i manaʻo ʻia. No laila, ua noiʻi ʻia ka hopena o ka hoʻohui ʻana o Gly ma ke kumu hoʻohālike kūpono loa o ka polymer hui PVA/Na Alg me ka hoʻohana ʻana i nā ʻano hana ʻelua hope loa: 3PVA-(C10)2Na Alg (i kapa ʻia ʻo 3PVA-2Na Alg no ka maʻalahi) a me ka Term 1 Na Alg − 3PVA-Mid 1 Na Alg. Wahi a ka palapala, hiki i ka PVA, NaAlg a me ka glycerol ke hana i nā pilina hydrogen nāwaliwali ma waena o nā hui hana hydroxyl. ʻOiai ʻo ka trimer PVA a me ka NaAlg a me ka glycerol dimer he nui nā hui OH, hiki ke hoʻokō ʻia ka pilina ma o kekahi o nā hui OH. Hōʻike ka Kiʻi 1 i ka pilina ma waena o ka mole glycerol kumu hoʻohālike a me ka molekala kumu hoʻohālike 3PVA-2Na Alg, a hōʻike ka Kiʻi 2 i ke kumu hoʻohālike i kūkulu ʻia o ka pilina ma waena o ka molekala kumu hoʻohālike Term 1Na Alg-3PVA-Mid 1Na Alg a me nā ʻano like ʻole o ka glycerol.
Nā ʻano hana i hoʻomaikaʻi ʻia: (a) Pili ʻo Gly a me 3PVA − 2Na Alg me (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, a me (f) 5 Gly.
Nā ʻano hana i hoʻomaikaʻi ʻia o ka Huaʻōlelo 1Na Alg-3PVA –Mid 1Na Alg e launa pū ana me (a) 1 Gly, (b) 2 Gly, (c) 3 Gly, (d) 4 Gly, (e) 5 Gly, a me (f) 6 Gly.
ʻO ka ikehu o ka electron band gap kahi mea nui e noʻonoʻo ai i ke aʻo ʻana i ka reactivity o kekahi mea electrode. No ka mea, wehewehe ia i ke ʻano o nā electrons ke hoʻololi ʻia ka mea i nā loli o waho. No laila, pono e kuhi i nā ikehu o ka electron band gap o HOMO/LUMO no nā ʻano āpau i aʻo ʻia. Hōʻike ka Papa 2 i nā loli i nā ikehu HOMO/LUMO o 3PVA-(C10)2Na Alg a me Term 1Na Alg − 3PVA- Mid 1Na Alg ma muli o ka hoʻohui ʻana o ka glycerol. Wahi a ref47, ʻo ka waiwai Eg o 3PVA-(C10)2Na Alg he 0.2908 eV, ʻoiai ʻo ka waiwai Eg o ka ʻano e hōʻike ana i ka hiki ke hana o ka lua o ka launa pū ʻana (ʻo ia hoʻi, Term 1Na Alg − 3PVA- Mid 1Na Alg) he 0.5706 eV.
Eia nō naʻe, ua ʻike ʻia ua hopena ka hoʻohui ʻana o ka glycerol i kahi loli iki i ka waiwai Eg o 3PVA-(C10)2Na Alg. I ka wā i launa pū ai ʻo 3PVA-(C10)2NaAlg me nā ʻāpana glycerol 1, 2, 3, 4 a me 5, ua lilo kona mau waiwai Eg i 0.302, 0.299, 0.308, 0.289 a me 0.281 eV, kēlā me kēia. Eia nō naʻe, aia kahi ʻike waiwai ma hope o ka hoʻohui ʻana i 3 mau ʻāpana glycerol, ua lilo ka waiwai Eg i liʻiliʻi ma mua o 3PVA-(C10)2Na Alg. ʻO ke kumu hoʻohālike e hōʻike ana i ka launa pū ʻana o 3PVA-(C10)2Na Alg me ʻelima mau ʻāpana glycerol ka kumu hoʻohālike launa pū ʻana. ʻO ia hoʻi, i ka piʻi ʻana o ka helu o nā ʻāpana glycerol, piʻi pū ka hiki ke launa pū.
I kēia manawa, no ka lua o ka hiki ke launa pū, ʻo nā ikehu HOMO/LUMO o nā molekala kumu hoʻohālike e hōʻike ana i ka 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 a me ka Term 1Na Alg − 3PVA –Mid 1Na Alg- 6Gly e lilo i 1.343, 1.34 7, 0.976, 0.607, 0.348 a me 0.496 eV, kēlā me kēia. Hōʻike ka Papa 2 i nā ikehu o ka hakahaka hui HOMO/LUMO i helu ʻia no nā ʻano āpau. Eia kekahi, ua hana hou ʻia ke ʻano like o nā hiki ke launa pū o ka hui mua ma ʻaneʻi.
ʻŌlelo ke kumumanaʻo band i ka physics solid state i ka emi ʻana o ka band gap o kahi mea electrode, piʻi ka conductivity uila o ka mea. ʻO ka doping kahi ʻano maʻamau e hōʻemi ai i ka band gap o nā mea sodium-ion cathode. Ua hoʻohana ʻo Jiang et al. i ka doping Cu e hoʻomaikaʻi i ka conductivity uila o nā mea papa β-NaMnO2. Ma ka hoʻohana ʻana i nā helu DFT, ua ʻike lākou ua hoʻemi ka doping i ka band gap o ka mea mai 0.7 eV a i 0.3 eV. Hōʻike kēia e hoʻomaikaʻi ana ka doping Cu i ka conductivity uila o ka mea β-NaMnO2.
Ua wehewehe ʻia ʻo MESP ʻo ia ka ikehu launa ma waena o ka hoʻolaha ʻana o ka uku molekala a me kahi uku maikaʻi hoʻokahi. Ua manaʻo ʻia ʻo MESP he mea hana kūpono no ka hoʻomaopopo ʻana a me ka wehewehe ʻana i nā waiwai kemika a me ka reactivity. Hiki ke hoʻohana ʻia ʻo MESP e hoʻomaopopo i nā ʻano hana o nā pilina ma waena o nā mea polymeric. Hōʻike ʻo MESP i ka hoʻolaha ʻana o ka uku i loko o ka hui ma lalo o ke aʻo ʻana. Eia kekahi, hāʻawi ʻo MESP i ka ʻike e pili ana i nā wahi hana i nā mea ma lalo o ke aʻo ʻana32. Hōʻike ka Kiʻi 3 i nā kiʻi MESP o 3PVA-(C10) 2Na Alg, 3PVA-(C10) 2Na Alg − 1Gly, 3PVA-(C10) 2Na Alg − 2Gly, 3PVA-(C10) 2Na Alg − 3Gly, 3PVA-(C10) 2Na Alg − 4Gly, a me 3PVA-(C10) 2Na Alg − 5Gly i wānana ʻia ma ka pae B3LYP/6-311G(d, p) o ke kumumanaʻo.
Nā ʻāpana MESP i helu ʻia me B3LYP/6-311 g(d, p) no (a) Gly a me 3PVA − 2Na Alg e launa pū ana me (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, a me (f) 5 Gly.
I kēia manawa, hōʻike ʻia ma ke Kiʻi 4 nā hopena i helu ʻia o MESP no ka Huaʻōlelo 1Na Alg- 3PVA – Mid 1Na Alg, Huaʻōlelo 1Na Alg- 3PVA – Mid 1Na Alg- 1Gly, Huaʻōlelo 1Na Alg- 3PVA – Mid 1Na Alg − 2Gly, Huaʻōlelo 1Na Alg- 3PVA – Mid 1Na Alg − 3gly, Huaʻōlelo 1Na Alg- 3PVA – Mid 1Na Alg − 4Gly, Huaʻōlelo 1Na Alg- 3PVA – Mid 1Na Alg- 5gly a me ka Huaʻōlelo 1Na Alg- 3PVA – Mid 1Na Alg − 6Gly, kēlā me kēia. Hōʻike ʻia ka MESP i helu ʻia ma ke ʻano he ʻano contour. Hōʻike ʻia nā laina contour e nā kala like ʻole. Hōʻike kēlā me kēia kala i kahi waiwai electronegativity like ʻole. Hōʻike ke kala ʻulaʻula i nā wahi electronegative kiʻekiʻe a reactive paha. I kēia manawa, hōʻike ke kala melemele i nā wahi neutral 49, 50, 51 i loko o ke ʻano. Ua hōʻike nā hopena MESP ua piʻi ka reactivity o 3PVA-(C10)2Na Alg me ka piʻi ʻana o ke kala ʻulaʻula a puni nā hiʻohiʻona i aʻo ʻia. I kēia manawa, ua emi ka ikaika o ke kala ʻulaʻula ma ka palapala ʻāina MESP o ka molekala hoʻohālike Term 1Na Alg-3PVA - Mid 1Na Alg ma muli o ka launa pū ʻana me nā ʻano glycerol like ʻole. Hōʻike ka loli o ka hoʻolaha kala ʻulaʻula a puni ke ʻano i manaʻo ʻia i ka reactivity, ʻoiai ʻo ka piʻi ʻana o ka ikaika e hōʻoia i ka piʻi ʻana o ka electronegativity o ka molekala hoʻohālike 3PVA-(C10)2Na Alg ma muli o ka piʻi ʻana o ka ʻike glycerol.
ʻO B3LYP/6-311 g(d, p) i helu ʻia ʻo MESP Term o 1Na Alg-3PVA-Mid 1Na Alg e launa pū ana me (a) 1 Gly, (b) 2 Gly, (c) 3 Gly, (d) 4 Gly, (e) 5 Gly, a me (f) 6 Gly.
Loaʻa i nā ʻōnaehana āpau i manaʻo ʻia kā lākou mau palena wela e like me ka enthalpy, entropy, ka mana wela, ka ikehu manuahi a me ka wela o ka hoʻokumu ʻana i helu ʻia ma nā mahana like ʻole ma ka pae mai 200 K a 500 K. No ka wehewehe ʻana i ke ʻano o nā ʻōnaehana kino, me ka hoʻopaʻa ʻana i kā lākou ʻano uila, pono nō hoʻi e aʻo i kā lākou ʻano wela ma ke ʻano he hana o ka mahana ma muli o kā lākou launa pū ʻana me kekahi, hiki ke helu ʻia me ka hoʻohana ʻana i nā kaulike i hāʻawi ʻia ma ka Papa 1. ʻO ke aʻo ʻana i kēia mau palena wela ua manaʻo ʻia he hōʻailona koʻikoʻi o ka pane ʻana a me ke kūpaʻa o ia mau ʻōnaehana kino ma nā mahana like ʻole.
No ka enthalpy o ka trimer PVA, hana mua ia me ka dimer NaAlg, a laila ma o ka hui OH i hoʻopili ʻia i ka ʻātoma kalapona #10, a ma hope me ka glycerol. ʻO Enthalpy ke ana o ka ikehu i loko o kahi ʻōnaehana thermodynamic. Ua like ka Enthalpy me ka wela holoʻokoʻa i loko o kahi ʻōnaehana, ʻo ia hoʻi ka ikehu kūloko o ka ʻōnaehana me ka huahana o kona nui a me ke kaomi. I nā huaʻōlelo ʻē aʻe, hōʻike ka enthalpy i ka nui o ka wela a me ka hana i hoʻohui ʻia a i ʻole i wehe ʻia mai kahi mea52.
Hōʻike ka Kiʻi 5 i nā loli enthalpy i ka wā o ka hopena o 3PVA-(C10)2Na Alg me nā ʻano glycerol like ʻole. Hōʻike nā pōkole A0, A1, A2, A3, A4, a me A5 i nā molekala hoʻohālike 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, a me 3PVA-(C10)2Na Alg − 5Gly, kēlā me kēia. Hōʻike ka Kiʻi 5a e piʻi ana ka enthalpy me ka piʻi ʻana o ka mahana a me ka nui o ka glycerol. ʻO ka enthalpy o ke ʻano e hōʻike ana i ka 3PVA-(C10)2NaAlg − 5Gly (ʻo ia hoʻi, A5) ma 200 K he 27.966 cal/mol, ʻoiai ʻo ka enthalpy o ke ʻano e hōʻike ana i ka 3PVA-2NaAlg ma 200 K he 13.490 cal/mol. ʻO ka hope loa, ʻoiai he maikaʻi ka enthalpy, he endothermic kēia hopena.
Ua wehewehe ʻia ʻo Entropy ma ke ʻano he ana o ka ikehu i loaʻa ʻole i loko o kahi ʻōnaehana thermodynamic pani a ua manaʻo pinepine ʻia he ana o ka haunaele o ka ʻōnaehana. Hōʻike ka Kiʻi 5b i ka loli o ka entropy o 3PVA-(C10)2NaAlg me ka mahana a pehea e launa pū ai me nā ʻāpana glycerol like ʻole. Hōʻike ka pakuhi e loli linearly ka entropy i ka piʻi ʻana o ka mahana mai 200 K a i 500 K. Hōʻike maopopo ka Kiʻi 5b i ka entropy o ke kumu hoʻohālike 3PVA-(C10)2Na Alg e pili ana i 200 cal/K/mol ma 200 K no ka mea hōʻike ka kumu hoʻohālike 3PVA-(C10)2Na Alg i ka liʻiliʻi o ka haunaele lattice. I ka piʻi ʻana o ka mahana, lilo ka kumu hoʻohālike 3PVA-(C10)2Na Alg i mea haunaele a wehewehe i ka piʻi ʻana o ka entropy me ka piʻi ʻana o ka mahana. Eia kekahi, ua maopopo he ʻoi aku ka waiwai entropy o ka ʻōnaehana o 3PVA-C10 2Na Alg-5 Gly.
ʻIke ʻia ke ʻano like ma ke Kiʻi 5c, e hōʻike ana i ka loli o ka mana wela me ka mahana. ʻO ka mana wela ka nui o ka wela e pono ai e hoʻololi i ka mahana o kahi nui o ka mea i hāʻawi ʻia e 1 °C47. Hōʻike ke Kiʻi 5c i nā loli o ka mana wela o ka molekole kumu hoʻohālike 3PVA-(C10)2NaAlg ma muli o nā pilina me nā ʻāpana glycerol 1, 2, 3, 4, a me 5. Hōʻike ke kiʻi e piʻi ana ka mana wela o ke kumu hoʻohālike 3PVA-(C10)2NaAlg me ka mahana. ʻO ka piʻi ʻana o ka mana wela i ʻike ʻia me ka piʻi ʻana o ka mahana e pili ana i nā haʻalulu wela phonon. Eia kekahi, aia nā hōʻike e alakaʻi ana ka hoʻonui ʻana i ka ʻike glycerol i ka hoʻonui ʻana i ka mana wela o ke kumu hoʻohālike 3PVA-(C10)2NaAlg. Eia kekahi, hōʻike ke ʻano he 3PVA-(C10)2NaAlg−5Gly ka waiwai mana wela kiʻekiʻe loa i hoʻohālikelike ʻia me nā ʻano ʻē aʻe.
Ua helu ʻia nā palena ʻē aʻe e like me ka ikehu manuahi a me ka wela hope loa o ka hoʻokumu ʻana no nā ʻano i aʻo ʻia a ua hōʻike ʻia ma ke Kiʻi 5d a me e, kēlā me kēia. ʻO ka wela hope loa o ka hoʻokumu ʻana, ʻo ia ka wela i hoʻokuʻu ʻia a i ʻole i omo ʻia i ka wā o ka hoʻokumu ʻana o kahi mea maʻemaʻe mai kona mau mea i hoʻohui ʻia ma lalo o ke kaomi mau. Hiki ke wehewehe ʻia ka ikehu manuahi ma ke ʻano he waiwai like me ka ikehu, ʻo ia hoʻi, pili kona waiwai i ka nui o ka mea i kēlā me kēia kūlana thermodynamic. ʻO ka ikehu manuahi a me ka wela o ka hoʻokumu ʻana o 3PVA-(C10)2NaAlg−5Gly ka mea haʻahaʻa loa a he -1318.338 a me -1628.154 kcal/mol, kēlā me kēia. I ka hoʻohālikelike ʻana, ʻo ke ʻano e hōʻike ana i ka 3PVA-(C10)2NaAlg ka mea i loaʻa ka ikehu manuahi kiʻekiʻe loa a me nā waiwai wela o ka hoʻokumu ʻana o -690.340 a me -830.673 kcal/mol, kēlā me kēia, i hoʻohālikelike ʻia me nā ʻano ʻē aʻe. E like me ka mea i hōʻike ʻia ma ke Kiʻi 5, ua loli nā ʻano thermal like ʻole ma muli o ka launa pū ʻana me ka glycerol. He maikaʻi ʻole ka ikehu manuahi Gibbs, e hōʻike ana ua paʻa ka ʻano i manaʻo ʻia.
Ua helu ʻo PM6 i nā palena wela o 3PVA- (C10) 2Na Alg maʻemaʻe (kumu hoʻohālike A0), 3PVA- (C10) 2Na Alg − 1 Gly (kumu hoʻohālike A1), 3PVA- (C10) 2Na Alg − 2 Gly (kumu hoʻohālike A2), 3PVA- (C10) 2Na Alg − 3 Gly (kumu hoʻohālike A3), 3PVA- (C10) 2Na Alg − 4 Gly (kumu hoʻohālike A4), a me 3PVA- (C10) 2Na Alg − 5 Gly (kumu hoʻohālike A5), kahi (a) ka enthalpy, (b) entropy, (c) ka hiki ke wela, (d) ka ikehu manuahi, a me (e) ka wela o ka hoʻokumu ʻana.
Ma ka ʻaoʻao ʻē aʻe, ʻo ke ʻano pilina ʻelua ma waena o ka PVA trimer a me ka dimeric NaAlg e kū nei ma nā hui OH terminal a me waena i loko o ka hoʻonohonoho PVA trimer. E like me ka hui mua, ua helu ʻia nā palena thermal me ka hoʻohana ʻana i ka pae like o ke kumumanaʻo. Hōʻike ka Kiʻi 6a-e i nā ʻano like ʻole o ka enthalpy, entropy, ka hiki ke wela, ka ikehu manuahi a, ʻo ka hope loa, ka wela o ka hoʻokumu ʻana. Hōʻike nā Kiʻi 6a-c e hōʻike ana ka enthalpy, entropy a me ka hiki ke wela o ka Term 1 NaAlg-3PVA-Mid 1 NaAlg i ke ʻano like me ka hui mua i ka wā e launa pū ai me nā ʻāpana glycerol 1, 2, 3, 4, 5 a me 6. Eia kekahi, piʻi mālie ko lākou mau waiwai me ka piʻi ʻana o ka mahana. Eia kekahi, ma ke kumu hoʻohālike Term 1 Na Alg − 3PVA-Mid 1 Na Alg i manaʻo ʻia, ua piʻi aʻe nā waiwai enthalpy, entropy a me ka hiki ke wela me ka piʻi ʻana o ka ʻike glycerol. Hōʻike nā pōkole B0, B1, B2, B3, B4, B5 a me B6 i nā ʻano hana ma lalo nei: Term 1 Na Alg − 3PVA- Mid 1 Na Alg, Term 1 Na Alg- 3PVA- Mid 1 Na Alg − 1 Gly, Term 1 Na Alg- 3PVA- Mid 1 Na Alg − 2gly, Term 1 Na Alg- 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 a me Term 1 Na Alg- 3PVA- Mid 1 Na Alg − 6 Gly. E like me ka mea i hōʻike ʻia ma ke Kiʻi 6a–c, ua maopopo ka piʻi ʻana o nā waiwai o ka enthalpy, entropy a me ka mana wela i ka piʻi ʻana o ka helu o nā ʻāpana glycerol mai 1 a i 6.
Ua helu ʻo PM6 i nā palena wela o ka Term 1 Na Alg- 3PVA- Mid 1 Na Alg (kumu hoʻohālike B0), Term 1 Na Alg- 3PVA- Mid 1 Na Alg – 1 Gly (kumu hoʻohālike B1), Term 1 Na Alg- 3PVA- Mid 1 Na Alg – 2 Gly (kumu hoʻohālike B2), Term 1 Na Alg- 3PVA- Mid 1 Na Alg – 3 Gly (kumu hoʻohālike B3), Term 1 Na Alg- 3PVA- Mid 1 Na Alg – 4 Gly (kumu hoʻohālike B4), Term 1 Na Alg- 3PVA- Mid 1 Na Alg – 5 Gly (kumu hoʻohālike B5), a me Term 1 Na Alg- 3PVA- Mid 1 Na Alg – 6 Gly (kumu hoʻohālike B6), me (a) enthalpy, (b) entropy, (c) ka hiki ke wela, (d) ikehu manuahi, a me (e) ka wela o ka hoʻokumu ʻana.
Eia kekahi, ʻo ka ʻano e hōʻike ana i ka Term 1 Na Alg- 3PVA- Mid 1 Na Alg- 6 Gly ka mea nona nā waiwai kiʻekiʻe loa o ka enthalpy, entropy a me ka mana wela i hoʻohālikelike ʻia me nā ʻano ʻē aʻe. I waena o lākou, ua piʻi ko lākou mau waiwai mai 16.703 cal/mol, 257.990 cal/mol/K a me 131.323 kcal/mol ma Term 1 Na Alg − 3PVA- Mid 1 Na Alg a i 33.223 cal/mol, 420.038 cal/mol/K a me 275.923 kcal/mol ma Term 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly, kēlā me kēia.
Eia nō naʻe, hōʻike nā Kiʻi 6d a me e i ka hilinaʻi ʻana o ka ikehu manuahi a me ka wela hope loa o ka hoʻokumu ʻana (HF) i ka mahana. Hiki ke wehewehe ʻia ʻo HF ʻo ia ka loli enthalpy e hana ʻia ke hoʻokumu ʻia kekahi mole o kahi mea mai kona mau mea ma lalo o nā kūlana kūlohelohe a me nā kūlana maʻamau. Ua maopopo mai ke kiʻi e hōʻike ana ka ikehu manuahi a me ka wela hope loa o ka hoʻokumu ʻana o nā ʻano āpau i aʻo ʻia i ka hilinaʻi linear ma ka mahana, ʻo ia hoʻi, e piʻi mālie a linearly lākou me ka piʻi ʻana o ka mahana. Eia kekahi, ua hōʻoia pū ke kiʻi ʻo ka ʻano e hōʻike ana i ka Term 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly ka ikehu manuahi haʻahaʻa loa a me ka HF haʻahaʻa loa. Ua emi nā ʻano ʻelua mai -758.337 a i -899.741 K cal/mol ma ka huaʻōlelo 1 Na Alg − 3PVA- Mid 1 Na Alg − 6 Gly a i -1,476.591 a me -1,828.523 K cal/mol. Ua maopopo mai nā hopena e emi ana ʻo HF me ka piʻi ʻana o nā ʻāpana glycerol. ʻO ke ʻano kēia, ma muli o ka hoʻonui ʻia ʻana o nā hui hana, piʻi pū ka reactivity a no laila emi ka ikehu e pono ai e hoʻokō i ka hopena. Hōʻoia kēia e hiki ke hoʻohana ʻia ka plasticized PVA/NaAlg i loko o nā pila ma muli o kona reactivity kiʻekiʻe.
Ma keʻano laulā, ua māhele ʻia nā hopena o ka mahana i ʻelua ʻano: nā hopena haʻahaʻa a me nā hopena wela kiʻekiʻe. ʻIke nui ʻia nā hopena o nā mahana haʻahaʻa ma nā ʻāina e noho ana ma nā latitudes kiʻekiʻe, e like me Greenland, Kanada, a me Rusia. I ka hoʻoilo, ʻoi aku ka mahana o ka ea ma waho ma kēia mau wahi ma lalo o ka zero degere Celsius. Hiki ke hoʻopilikia ʻia ke ola a me ka hana o nā pila lithium-ion e nā mahana haʻahaʻa, ʻoiai nā mea i hoʻohana ʻia i nā kaʻa uila hybrid plug-in, nā kaʻa uila maʻemaʻe, a me nā kaʻa uila hybrid. ʻO ka huakaʻi lewa kekahi ʻano anuanu e pono ai nā pila lithium-ion. No ka laʻana, hiki i ka mahana ma Mars ke hāʻule i -120 degere Celsius, kahi e hōʻeha nui ai i ka hoʻohana ʻana i nā pila lithium-ion i nā mokulele. Hiki i nā mahana hana haʻahaʻa ke alakaʻi i ka emi ʻana o ka helu hoʻoili uku a me ka hana hopena kemika o nā pila lithium-ion, e hopena ana i ka emi ʻana o ka helu hoʻolaha o nā ion lithium i loko o ka electrode a me ka conductivity ionic i loko o ka electrolyte. ʻO kēia hōʻino ʻana ka hopena i ka emi ʻana o ka hiki ke ikehu a me ka mana, a i kekahi manawa ua emi iho ka hana53.
ʻIke ʻia ka hopena wela kiʻekiʻe ma kahi ākea o nā wahi noi, me nā wahi wela kiʻekiʻe a me nā wahi wela haʻahaʻa, ʻoiai ʻo ka hopena wela haʻahaʻa e kaupalena nui ʻia i nā wahi noi wela haʻahaʻa. Hoʻoholo nui ʻia ka hopena wela haʻahaʻa e ka mahana ambient, ʻoiai ʻoi aku ka pololei o ka hopena wela kiʻekiʻe i nā mahana kiʻekiʻe i loko o ka pākahiko lithium-ion i ka wā o ka hana.
Hoʻopuka nā pila Lithium-ion i ka wela ma lalo o nā kūlana o kēia au kiʻekiʻe (me ka hoʻouka wikiwiki ʻana a me ka hoʻokuʻu wikiwiki ʻana), kahi e piʻi ai ka mahana o loko. Hiki i ka ʻike ʻana i nā mahana kiʻekiʻe ke hoʻohaʻahaʻa i ka hana o ka pila, me ka nalowale o ka hiki a me ka mana. ʻO ka maʻamau, ʻo ka nalowale ʻana o ka lithium a me ka hoʻihoʻi ʻana o nā mea hana i nā mahana kiʻekiʻe e alakaʻi ai i ka nalowale o ka hiki, a ʻo ka nalowale o ka mana ma muli o ka piʻi ʻana o ke kū'ē kūloko. Inā puka ka mahana ma waho o ke kaohi, hana ʻia ka holo ʻana o ka thermal, a i kekahi mau hihia hiki ke alakaʻi i ka puhi koke ʻana a i ʻole ka pahū ʻana.
ʻO nā helu QSAR kahi ʻano hana hoʻohālikelike helu a makemakika paha i hoʻohana ʻia e ʻike i nā pilina ma waena o ka hana olaola a me nā waiwai kūkulu o nā hui. Ua hoʻomaikaʻi ʻia nā molekala i hoʻolālā ʻia a ua helu ʻia kekahi mau waiwai QSAR ma ka pae PM6. Hōʻike ka Papa 3 i kekahi o nā wehewehe QSAR i helu ʻia. ʻO nā hiʻohiʻona o ia mau wehewehe he uku, TDM, ikehu holoʻokoʻa (E), hiki ke ionization (IP), Log P, a me ka polarizability (e ʻike i ka Papa 1 no nā haʻilula e hoʻoholo ai i ka IP a me Log P).
Hōʻike nā hopena helu ʻana he ʻole ka uku holoʻokoʻa o nā ʻano āpau i aʻo ʻia no ka mea aia lākou ma ke kūlana honua. No ka hiki ke launa pū mua, ʻo ka TDM o ka glycerol he 2.788 Debye a me 6.840 Debye no 3PVA-(C10) 2Na Alg, ʻoiai ua hoʻonui ʻia nā waiwai TDM i 17.990 Debye, 8.848 Debye, 5.874 Debye, 7.568 Debye a me 12.779 Debye i ka wā i launa pū ai ʻo 3PVA-(C10) 2Na Alg me 1, 2, 3, 4 a me 5 mau ʻāpana o ka glycerol. ʻO ke kiʻekiʻe o ka waiwai TDM, ʻo ke kiʻekiʻe o kona reactivity me ke kaiapuni.
Ua helu ʻia hoʻi ka ikehu holoʻokoʻa (E), a ua ʻike ʻia nā waiwai E o ka glycerol a me 3PVA-(C10)2 NaAlg he -141.833 eV a me -200092.503 eV, kēlā me kēia. I kēia manawa, ʻo nā ʻano e hōʻike ana i ka 3PVA-(C10)2 NaAlg e launa pū me nā ʻāpana glycerol 1, 2, 3, 4 a me 5; lilo ʻo E i -996.837, -1108.440, -1238.740, -1372.075 a me -1548.031 eV, kēlā me kēia. ʻO ka hoʻonui ʻana i ka ʻike glycerol e alakaʻi i ka emi ʻana o ka ikehu holoʻokoʻa a no laila e hoʻonui i ka reactivity. Ma muli o ka helu ʻana o ka ikehu holoʻokoʻa, ua hoʻoholo ʻia ʻo ka molekala hoʻohālike, ʻo ia hoʻi ʻo 3PVA-2Na Alg-5 Gly, ʻoi aku ka reactive ma mua o nā molekala hoʻohālike ʻē aʻe. Pili kēia hanana i ko lākou ʻano. ʻElua wale nō hui -COONa i loko o 3PVA-(C10)2NaAlg, ʻoiai ʻelua mau hui -COONa i loko o nā ʻano hana ʻē aʻe akā he nui nā hui OH i loaʻa iā lākou, ʻo ia hoʻi, ua hoʻonui ʻia ko lākou pane ʻana i ke kaiapuni.
Eia kekahi, ua noʻonoʻo ʻia nā ikehu ionization (IE) o nā ʻano āpau i loko o kēia haʻawina. ʻO ka ikehu ionization kahi palena koʻikoʻi no ke ana ʻana i ka reactivity o ke kumu hoʻohālike i aʻo ʻia. ʻO ka ikehu e pono ai e hoʻoneʻe i kahi electron mai kekahi wahi o kahi mole a i ka palena ʻole ua kapa ʻia ʻo ka ikehu ionization. Hōʻike ia i ke kekelē o ka ionization (ʻo ia hoʻi ka reactivity) o ka mole. ʻO ke kiʻekiʻe o ka ikehu ionization, ʻo ka haʻahaʻa o ka reactivity. ʻO nā hopena IE o 3PVA-(C10)2NaAlg e launa pū ana me nā ʻāpana glycerol 1, 2, 3, 4 a me 5 he -9.256, -9.393, -9.393, -9.248 a me -9.323 eV, kēlā me kēia, ʻoiai ʻo nā IE o glycerol a me 3PVA-(C10)2NaAlg he -5.157 a me -9.341 eV, kēlā me kēia. ʻOiai ʻo ka hoʻohui ʻana o ka glycerol i hopena i ka emi ʻana o ka waiwai IP, ua piʻi aʻe ka hana hoʻololi molekala, kahi e hoʻonui ai i ka hoʻohana ʻana o ka molekala hoʻohālike PVA/NaAlg/glycerol i nā mea hana electrochemical.
ʻO ka wehewehe ʻelima ma ka Papa 3 ʻo Log P, ʻo ia ka logarithm o ka coefficient mahele a hoʻohana ʻia e wehewehe inā he hydrophilic a hydrophobic paha ke ʻano e aʻo ʻia nei. ʻO ka waiwai Log P maikaʻi ʻole e hōʻike ana i kahi mole hydrophilic, ʻo ia hoʻi, hoʻoheheʻe maʻalahi ia i ka wai a hoʻoheheʻe maikaʻi ʻole i nā mea hoʻoheheʻe organik. ʻO ka waiwai maikaʻi e hōʻike ana i ke kaʻina hana ʻē aʻe.
Ma muli o nā hopena i loaʻa, hiki ke hoʻoholo ʻia he hydrophilic nā ʻano āpau, ʻoiai ʻo kā lākou mau waiwai Log P (3PVA-(C10)2Na Alg − 1Gly, 3PVA-(C10)2Na Alg − 2Gly, 3PVA-(C10)2Na Alg − 3Gly, 3PVA-(C10)2Na Alg − 4Gly a me 3PVA-(C10)2Na Alg − 5Gly) he -3.537, -5.261, -6.342, -7.423 a me -8.504, kēlā me kēia, ʻoiai ʻo ka waiwai Log P o ka glycerol he -1.081 wale nō a ʻo 3PVA-(C10)2Na Alg he -3.100 wale nō. ʻO ke ʻano kēia e loli nā waiwai o ke ʻano e aʻo ʻia nei i ka wā e hoʻokomo ʻia ai nā molekala wai i loko o kona ʻano.
ʻO ka mea hope loa, ua helu ʻia nā polarizability o nā ʻano āpau ma ka pae PM6 me ka hoʻohana ʻana i kahi ʻano semi-empirical. Ua ʻike mua ʻia ʻo ka polarizability o ka hapa nui o nā mea e pili ana i nā kumu like ʻole. ʻO ka mea nui loa ka nui o ke ʻano ma lalo o ke aʻo ʻana. No nā ʻano āpau e pili ana i ke ʻano mua o ka launa pū ʻana ma waena o 3PVA a me 2NaAlg (hana ʻia ka launa pū ʻana ma o ka helu atom carbon 10), hoʻomaikaʻi ʻia ka polarizability e ka hoʻohui ʻana o ka glycerol. Hoʻonui ka polarizability mai 29.690 Å a i 35.076, 40.665, 45.177, 50.239 a me 54.638 Å ma muli o nā launa pū ʻana me nā ʻāpana glycerol 1, 2, 3, 4 a me 5. No laila, ua ʻike ʻia ʻo ka molekala hoʻohālike me ka polarizability kiʻekiʻe loa ʻo 3PVA-(C10)2NaAlg−5Gly, ʻoiai ʻo ka molekala hoʻohālike me ka polarizability haʻahaʻa loa ʻo 3PVA-(C10)2NaAlg, ʻo ia hoʻi he 29.690 Å.
Ua hōʻike ka loiloi o nā wehewehe QSAR ʻo ke ʻano e hōʻike ana i ka 3PVA-(C10)2NaAlg − 5Gly ka mea pane nui loa no ka launa pū mua i manaʻo ʻia.
No ke ʻano launa pū ʻelua ma waena o ka trimer PVA a me ka dimer NaAlg, hōʻike nā hopena ua like kā lākou mau uku me nā mea i manaʻo ʻia ma ka ʻāpana ma mua no ka launa pū mua. ʻAʻohe uku uila o nā ʻano āpau, ʻo ia hoʻi aia lākou a pau ma ke kūlana honua.
E like me ka mea i hōʻike ʻia ma ka Papa 4, ua piʻi aʻe nā waiwai TDM (i helu ʻia ma ka pae PM6) o ka Term 1 Na Alg − 3PVA-Mid 1 Na Alg mai 11.581 Debye a i 15.756, 19.720, 21.756, 22.732, 15.507, a me 15.756 i ka wā i pane ai ka Term 1 Na Alg − 3PVA-Mid 1 Na Alg me 1, 2, 3, 4, 5, a me 6 mau ʻāpana o ka glycerol. Eia nō naʻe, emi iho ka ikehu holoʻokoʻa me ka piʻi ʻana o ka helu o nā ʻāpana glycerol, a i ka wā e launa pū ai ʻo Term 1 Na Alg − 3PVA- Mid 1 Na Alg me kahi helu o nā ʻāpana glycerol (1 a 6), ʻo ka ikehu holoʻokoʻa he − 996.985, − 1129.013, − 1267.211, − 1321.775, − 1418.964, a me − 1637.432 eV, kēlā me kēia.
No ka lua o ka hiki ke launa pū, ua helu ʻia ʻo IP, Log P a me ka polarizability ma ka pae PM6 o ke kumumanaʻo. No laila, ua noʻonoʻo lākou i ʻekolu mau wehewehe ikaika loa o ka reactivity molecular. No nā ʻano e hōʻike ana i ka End 1 Na Alg-3PVA-Mid 1 Na Alg e launa pū ana me nā ʻāpana glycerol 1, 2, 3, 4, 5 a me 6, piʻi ka IP mai −9.385 eV a i −8.946, −8.848, −8.430, −9.537, −7.997 a me −8.900 eV. Eia nō naʻe, ua haʻahaʻa ka waiwai Log P i helu ʻia ma muli o ka plasticization o End 1 Na Alg-3PVA-Mid 1 Na Alg me ka glycerol. I ka piʻi ʻana o ka nui o ka glycerol mai 1 a 6, lilo kona mau waiwai i -5.334, -6.415, -7.496, -9.096, -9.861 a me -10.53 ma kahi o -3.643. ʻO ka mea hope loa, ua hōʻike ka ʻikepili polarizability ua hopena ka hoʻonui ʻana i ka nui o ka glycerol i ka hoʻonui ʻana i ka polarizability o Term 1 Na Alg- 3PVA- Mid 1 Na Alg. Ua piʻi ka polarizability o ka molekala hoʻohālike Term 1 Na Alg- 3PVA- Mid 1 Na Alg mai 31.703 Å a i 63.198 Å ma hope o ka launa pū ʻana me 6 mau ʻāpana glycerol. He mea nui e hoʻomaopopo ʻia e hoʻonui ʻia ka helu o nā ʻāpana glycerol i ka lua o ka manawa e launa pū ai e hōʻoia ʻoiai ka nui o nā ʻātoma a me ke ʻano paʻakikī, ua hoʻomaikaʻi ʻia ka hana me ka hoʻonui ʻana o ka nui o ka glycerol. No laila, hiki ke ʻōlelo ʻia e hiki i ke kumu hoʻohālike PVA/Na Alg/glycerin i loaʻa ke pani hapa i nā pila lithium-ion, akā pono hou aku ka noiʻi a me ka hoʻomohala ʻana.
ʻO ke ʻano o ka hiki ke hoʻopaʻa ʻia o kahi ʻili i kahi adsorbate a me ka loiloi ʻana i nā pilina kūikawā ma waena o nā ʻōnaehana e pono ai ka ʻike o ke ʻano o ka pilina e kū nei ma waena o kekahi mau ʻātoma ʻelua, ka paʻakikī o nā pilina intermolecular a me intramolecular, a me ka hoʻolaha ʻana o ka nui o ka electron o ka ʻili a me ka adsorbent. ʻO ka nui o ka electron ma ke kiko koʻikoʻi o ka pilina (BCP) ma waena o nā ʻātoma e launa pū ana he mea koʻikoʻi no ka loiloi ʻana i ka ikaika o ka pilina ma ka loiloi QTAIM. ʻO ke kiʻekiʻe o ka nui o ka hoʻopiʻi electron, ʻoi aku ka paʻa o ka pilina covalent a, ma ke ʻano laulā, ʻoi aku ke kiʻekiʻe o ka nui o ka electron ma kēia mau kiko koʻikoʻi. Eia kekahi, inā ʻoi aku ka liʻiliʻi o ka nui o ka ikehu electron (H(r)) a me ka nui o ka hoʻopiʻi Laplace (∇2ρ(r)) ma mua o 0, hōʻike kēia i ke alo o nā pilina covalent (laulā). Ma ka ʻaoʻao ʻē aʻe, i ka wā ʻoi aku ka nui o ∇2ρ(r) a me H(r) ma mua o 0.54, hōʻike ia i ke alo o nā pilina non-covalent (pani pani) e like me nā pilina hydrogen nāwaliwali, nā ikaika van der Waals a me nā pilina electrostatic. Ua hōʻike ka loiloi QTAIM i ke ʻano o nā pilina non-covalent i loko o nā ʻano i aʻo ʻia e like me ka mea i hōʻike ʻia ma nā Kiʻi 7 a me 8. Ma muli o ka loiloi, ua hōʻike nā molekala hoʻohālike e hōʻike ana i ka 3PVA − 2Na Alg a me Term 1 Na Alg − 3PVA –Mid 1 Na Alg i ke kūpaʻa kiʻekiʻe ma mua o nā molekala e launa pū ana me nā ʻāpana glycine like ʻole. ʻO kēia no ka mea he nui nā pilina non-covalent i ʻoi aku ka nui ma ka ʻano alginate e like me nā pilina electrostatic a me nā pilina hydrogen e hiki ai i ka alginate ke hoʻopaʻa i nā composites. Eia kekahi, hōʻike kā mākou mau hopena i ke koʻikoʻi o nā pilina non-covalent ma waena o nā molekala hoʻohālike 3PVA − 2Na Alg a me Term 1 Na Alg − 3PVA –Mid 1 Na Alg a me glycine, e hōʻike ana he kuleana koʻikoʻi ko glycine i ka hoʻololi ʻana i ke kaiapuni uila holoʻokoʻa o nā composites.
Ka loiloi QTAIM o ka molekole kumu hoʻohālike 3PVA − 2NaAlg e launa pū ana me (a) 0 Gly, (b) 1 Gly, (c) 2 Gly, (d) 3 Gly, (e) 4 Gly, a me (f) 5Gly.