He nui nā pono o nā electrolytes paʻa ma mua o nā electrolytes wai. No ka laʻana, hiki iā lākou ke hoʻēmi i ka deformation electrode i ka wā o ka hoʻouka ʻana a me ka hoʻokuʻu ʻana, hoʻomaikaʻi i ka palekana. Loaʻa iā lākou kahi kūpaʻa maikaʻi loa, maʻalahi ka hana, a me ka ulu ʻana olithiumHiki ke ho'emi 'ia nā dendrites ma ka solvent{0}}free solid polymer electrolytes.
Ua hoʻomaka ka noiʻi ʻana i nā electrolytes polymer i ka makahiki 1973, i ka wā i hoʻomaka ai ʻo Fenton et al. Ua ʻike ʻia e hiki i nā paʻipaʻi polyethylene oxide (PEO) me nā metala alkali ke alakaʻi i nā ion. Mai ia manawa, ua ʻike nui ʻia nā electrolytes polymer.
I ka makahiki 1978, ua wānana ʻo Kauka Armand e hiki ke hoʻohana ʻia ka PEO-state solid{3}}electrolytes ma ke ʻano he electrolytes no nā pā.
I loko o nā makahiki ʻelua e hiki mai ana, ua hoʻoikaika nui ka poʻe noiʻi i ke aʻo ʻana i ke ʻano o ka lawe ʻana i ka ion a me nā waiwai physicochemical o ka palena electrolyte-electrode i loko o ka pākaukau, a ua holomua maikaʻi.
Hiki i nā ʻakika Lithium-ion me ka hoʻohana ʻana i nā electrolytes polymer paʻa ke pale i nā pilikia leaka e pili ana i nā wai electrolytes.
He maʻalahi ka hana ʻana o nā polymers a hiki ke hoʻoemi ʻia. Ma muli o ko lākou ʻilikai kiʻekiʻe, hiki ke hoʻohana ʻia nā polymers no ka hana ʻana i nā ʻeke kiʻiʻoniʻoni lahilahi. Hiki ke hana ʻia nā ʻano hana pākaukau me ka hoʻohana ʻana i nā electrolytes polymer e hoʻokō i nā koi noi. Eia kekahi, hāʻawi ka polymer electrolytes i ke kemika kiʻekiʻe, electrochemical, a me ka thermal stability i hoʻohālikelike ʻia i nā electrolytes wai, me ka liʻiliʻi o nā ʻaoʻao ʻaoʻao me nā electrodes a me kahi ākea ākea o ka hana. Hiki i ka maʻalahi o nā electrolytes polymer ke hoʻololi i nā loli i nā electrodes i ka wā o ka hoʻouka ʻana a me ka hoʻokuʻu ʻana, e hoʻopaʻa ana i ke ʻano o ka pākaukau. No laila, ma hope o ka ho'olaha 'ana i nā 'akika wai-iona, e ulu koke ana ka 'ike loea pila lithium-ion ma muli o ka polymer electrolytes a e ho'okō i ka 'oihana kalepa.
Nui nā ʻano no ka hoʻokaʻawale ʻana i nā electrolytes polymer, a ʻokoʻa nā kūlana. I kēia manawa, hoʻokaʻawale ʻia nā electrolytes polymer paʻa e like me ke ʻano o ka polymer i hoʻohana ʻia, e like me ka polyether-polyethylene oxide (PEO) kaulana loa, a me ka polymethyl methacrylate (PMMA) a me ka polyacrylonitrile (PAN). Ma ka ʻōlelo maʻamau, pono nā polimer electrolytes e hoʻokō i nā kūlana i hiki ke hoʻohana pono ʻia i loko o nā pākahi lithium{3}}ion.
Kiʻekiʻe ionic conductivity
Nui ka helu hoʻoili lithium-ion
ʻO ka ikaika mechanical maikaʻi
puka aniani electrochemical ākea
Paʻa kemika maikaʻi a me ka wela
Ma nā ʻōnaehana electrolyte polymer i kēia manawa, hōʻike nā polymers i ka crystallinity koʻikoʻi ma ka wela lumi, e wehewehe ana i ke kumu o ka haʻahaʻa o ka conductivity o nā electrolytes polymer solid ma ka wela o ka lumi ma mua o nā electrolytes wai. ʻO ka hapa nui o nā kristal i nā polymers he spherulites, me nā ʻāpana amorphous ma waena o lākou. Manaʻo ʻia ʻo ka lithium -ion conduction ma kēia mau ʻāpana amorphous.
No laila, he mea kōkua ka hoʻomaopopo ʻana i ke ʻano o nā polymers no ke aʻo ʻana i ke ʻano hana hoʻoiho lithium-ion.
No nā ʻōnaehana electrolyte polymer binary, ʻelua mau ʻano o ka hoʻolālā pae: nā ʻāpana crystalline a me nā ʻāpana amorphous. ʻO ka hoʻokumu ʻana i nā ʻāpana crystalline e hoʻokele kinetically a pili pono i nā kūlana hoʻomākaukau kūikawā a me ka manawa. ʻO ka ʻōlelo koʻikoʻi, ma muli o ka loaʻa ʻana o nā ʻāpana crystalline i loko o ka ʻōnaehana polymer, a me ka loli nui o kēia mau ʻāina me nā kūlana like ʻole, ʻaʻole ʻepekema loa ka hoʻohālikelike ʻana i ka conductivity o nā ʻano electrolytes polymer. Eia nō naʻe, ma lalo o kekahi mau kūlana, inā lohi ka ulu ʻana o nā ʻāpana crystalline a ʻo ka deviation o ka ionic conductivity i loko o kahi ākea ʻae ʻia, ʻae ʻia ka hoʻohālikelike ʻana i ka conductivity. ʻO ia ke kumu e hoʻohālikelike pinepine ai mākou i nā hopena like ʻole.
No ka mea, pili i ka manawa-ka ulu ana o na spherulites i loko o ka polimer, pili ka manawa-ka hookui ionic ma na mahana ma lalo o ka helu hehee o ka polymer. Eia kekahi, pili ka lithium-ion conductivity o nā polymer electrolytes i ka nui o ka hoʻomehana ʻana, ka nui o ka hoʻomaha ʻana, a me ka manawa hoʻomaha. No ka laʻana, ʻoi aku ka lōʻihi o ka manawa hoʻomaha i kahi ʻano polimer piha piha a me ka crystallinity kiʻekiʻe, e alakaʻi ana i ka emi mālie o ka conductivity ionic i ka liʻiliʻi me ka hoʻonui ʻana i ka manawa hoʻomaha. Pēlā nō, ʻoi aku ka maikaʻi o ka hoʻoluʻu ʻana i ka crystallization, a ʻo ka conductivity ionic e like me ka emi ʻana i ka liʻiliʻi.
Ke lawe nei i ka binary solid polymer electrolyte o PEO a me LiCIO4 ma ke ʻano he laʻana, ua loaʻa i kēia ʻano nā hale hana he nui. ʻO ka mua, hiki iā LiClO4 a me PEO ke hana i nā paʻakikī like ʻole, me PEO6-LiCIO4, PEO3-LiCIO4, PEO2-LiCIO4, a me PEO-LiClO4. Ma waena o lākou, i ka wā O:Li=10:1, hiki i ka PEO6-LiCIO4 ke hana i kahi eutectic me PEO, me kahi helu hehee o 50 degere . Eia kekahi, ke hoʻokiʻekiʻe ka mahana i 160 degere, hiki ke hana i kahi eutectic nui. I loko o ke kaʻina hoʻoluʻu, e hoʻopuka ka eutectic nui i ʻekolu mau ʻano spherulites: ʻo ka ʻano mua e hoʻoheheʻe ʻia ma luna o 120 degere a loaʻa ka paʻakai kiʻekiʻe; ʻo ka lua o ka ʻano heheʻe ma waena o 45 a me 60 degere, he haʻahaʻa ka paʻakai paʻakai, a hana mālie; ʻo ke kolu o ke ʻano he wahi heheʻe haʻahaʻa iki ma mua o ka polymer host a ʻoi aku ka wikiwiki. Manaʻo ka noiʻi a me ka nānā ʻana: ʻo ke ʻano mua o ka spherulite he PEO3-LiCIO4; ʻo ka lua o ka ʻano he hui pū ʻia o PEO-LiCIO4 a me PEO3-LiCIO4 complexes; a ʻo ke ʻano ʻekolu e pili ana i ka PEO ponoʻī. Eia kekahi, hiki i ka paʻakai lithium a me ke kaʻina hana wela ke alakaʻi i nā loli hoʻololi.
ʻO ka polymer electrolytes kahi papa o nā mea polymer hana me ka conductivity ionic kiʻekiʻe, i hana ʻia e nā hopena paʻakikī ma waena o nā polymers a me nā paʻakai metala e hoʻohana ana i nā polymers ma ke ʻano he matrix. Ma muli o ka polimer matrix, loa'a nā polimer electrolytes ma'amau i ka PEO-polymer electrolytes, PVDE-polymer electrolytes, PMMA-polymer electrolytes, a me nā mea 'ē a'e. 'A'ole e like me nā mea electrolytes mānoanoa pa'a 'ole{5}}, 'ano māmā, elastic, a pa'a ka polymer electrolytes. E like me nā electrolytes state solid inorganic, ʻaʻole wale nā electrolytes polymer e hoʻokele i nā ion i loko o nā ʻeke lithium-ion akā hana pū kekahi ma ke ʻano he mea hoʻokaʻawale pākahi. Loaʻa i ka polymer electrolytes ka nui o nā pono penei:
Hiki iā ia ke hoʻoponopono maikaʻi i ka pilikia o ka hoʻokumu ʻana i ka lithium dendrite i loko o nā pākahi lithium-ion
Hiki iā ia ke hoʻololi maikaʻi i ka hoʻololi ʻana i ka wā o ka hoʻouka ʻana a me ka hoʻokuʻu ʻana o nā ʻaniani lithium-
Hiki iā ia ke hōʻemi a hoʻopau paha i ka hopena kemika ma waena o nā mea electrolyte a me nā mea electrode i loko o nā ʻakika lithium{0}}ion.
Loaʻa iā ia ka hana palekana kiʻekiʻe
ʻO nā complexes i hana ʻia e nā paʻakai lithium like ʻole (me LBF4, LIPF6, LiCFSO4, a me LiASF6) me ka PEO, ua like ke ʻano me nā mea i hana ʻia e LiCIO4, ʻo ia hoʻi, ʻaʻohe hopena pololei o ke ʻano o ka paʻakai lithium i ke ʻano o ka paʻakikī i hana ʻia me PEO. Ma ke kiko'ī, hiki i ka LiBF ke hana i 'elua pa'akikī me PEO: PEO4-LIBF a me PEO,S-LiBF. Aia ka ratio O/Li ma waena o 16 a me 20, hiki i ka PEO2.5-LIBF4 ke hana i ka eutectic me PEO. Hiki iā LPF6 ke hana i ʻelua paʻakikī me PEO: PEO6-LiPF6 a me PEO:-LiPF6. ʻO nā paʻakikī ʻelua i hoʻokumu ʻia e LiASF6 me PEO ua like ia me nā LiPF6, akā me nā helu heheʻe kiʻekiʻe. Hiki i nā paʻakai lithium anion nui ke hana i nā paʻakikī me PEO, akā ʻoi aku ka lohi o nā kinetics. Eia kekahi, pili ke kaomi i ka ulu ʻana o ka kristal i kekahi ʻano. Hoʻonui ka piʻi kiʻekiʻe i ka ulu ʻana o ka spherulite, hoʻemi i ka ʻāina amorphous, a me ka hoʻemi ʻana i ka conductivity lithium-ion.