Ci gaban batirin lithium

Asalin na'urar baturi na iya farawa tare da gano kwalbar Leiden. Masanin kimiyya dan kasar Holland Pieter van Musschenbroek ne ya fara kirkiro kwalaben Leiden a shekara ta 1745. Leyden jar na'ura ce ta zamani mai karfin wuta. Ya ƙunshi zanen ƙarfe guda biyu wanda insulator ya raba. Ana amfani da sandar ƙarfe da ke sama don adanawa da sakin caji. Lokacin da ka taɓa sanda Lokacin da ake amfani da ƙwallon ƙarfe, kwalban Leiden na iya kiyayewa ko cire makamashin lantarki na ciki, kuma ƙa'idarsa da shirye-shiryensa suna da sauƙi. Duk mai sha'awar zai iya yin shi da kansa a gida, amma yanayin fitar da kansa ya fi tsanani saboda jagorar sauƙi. Gabaɗaya, za a kashe duk wutar lantarki a cikin sa'o'i kaɗan zuwa ƴan kwanaki. Koyaya, fitowar kwalbar Leiden alama ce ta sabon mataki a cikin binciken wutar lantarki.

A cikin 1790s, masanin kimiyya dan Italiya Luigi Galvani ya gano amfani da zinc da wayoyi na jan karfe don haɗa kafafun kwadi kuma ya gano cewa kafafun kwadi za su yi rawar jiki, don haka ya ba da shawarar manufar "bioelectricity." Wannan binciken ya sa masanin kimiyya dan kasar Italiya Alessandro ya girgiza. Rashin amincewar Volta, Volta ya yi imanin cewa murƙushe ƙafafuwar kwaɗo ya fito ne daga wutar lantarki da ƙarfe ke samarwa maimakon wutar lantarkin da ke kan kwaɗo. Don karyata ka'idar Galvani, Volta ya ba da shawarar shahararren Volta Stack. Tarin voltaic ya ƙunshi tulun zinc da tagulla tare da kwali da aka jiƙa a cikin ruwan gishiri a tsakani. Wannan shine samfurin batirin sinadari da aka gabatar.
Ma'aunin amsawar lantarki na tantanin halitta voltaic:

tabbataccen lantarki: 2H^++2e^-→H_2

korau electrode: Zn→〖Zn〗^(2+)+2e^-

A cikin 1836, masanin kimiyar Burtaniya John Frederic Daniell ya ƙirƙira batirin Daniel don magance matsalar kumfa na iska a cikin baturi. Batirin Daniel yana da sigar farko ta batirin sinadarai na zamani. Ya ƙunshi sassa biyu. Sashin tabbatacce yana nutsar da shi a cikin maganin jan karfe sulfate. Wani ɓangaren jan ƙarfe shine zinc da aka nutsar a cikin maganin zinc sulfate. Asalin baturin Daniel an cika shi da maganin sulfate na jan karfe a cikin tulun tagulla kuma an saka kwandon yumbu mai yumbu a tsakiya. A cikin wannan akwati na yumbu, akwai sandar zinc da zinc sulfate a matsayin wutar lantarki mara kyau. A cikin maganin, ƙananan ramuka a cikin kwandon yumbura suna ba da damar maɓallan biyu don musayar ions. Batura Daniel na zamani galibi suna amfani da gadoji na gishiri ko maɓalli masu yuwuwa don cimma wannan tasirin. An yi amfani da batir Daniel azaman tushen wutar lantarki don hanyar sadarwar telegraph har sai busassun batura ya maye gurbinsu.

Ma'aunin amsawar lantarki na batirin Daniel:

Na'ura mai inganci: 〖Cu〗^(2+)+2e^-→Cu

korau electrode: Zn→〖Zn〗^(2+)+2e^-

Ya zuwa yanzu, an ƙayyade ainihin nau'in baturi, wanda ya haɗa da ingantacciyar lantarki, rashin wutar lantarki, da kuma electrolyte. A kan irin wannan, batura sun sami ci gaba cikin sauri a cikin shekaru 100 masu zuwa. Sabbin tsarin batir da yawa sun bayyana, ciki har da masanin kimiyyar Faransa Gaston Planté ya ƙirƙira batir-acid na gubar a cikin 1856. Batirin gubar-acid Yawan fitowar sa na yanzu da ƙarancin farashi sun ja hankalin jama'a sosai, don haka ana amfani da shi a yawancin na'urorin hannu, kamar farkon wutar lantarki. ababan hawa. Yawancin lokaci ana amfani da shi azaman madadin wutar lantarki ga wasu asibitoci da tashoshi na tushe. Batirin gubar-acid galibi sun ƙunshi gubar, gubar dioxide, da kuma maganin sulfuric acid, kuma ƙarfin ƙarfinsu na iya kaiwa kusan 2V. Ko a zamanin yau, ba a kawar da batirin gubar-acid ba saboda manyan fasaharsu, ƙarancin farashi, da tsarin tushen ruwa mai aminci.

Ma'aunin amsawar electrode na baturin gubar-acid:

Positive electrode: PbO_2+〖SO〗_4^(2-)+4H^++2e^-→Pb〖SO〗_4+2H_2 O

Negative electrode: Pb+〖SO〗_4^(2-)→Pb〖SO〗_4+2e^-

Baturin nickel-cadmium, wanda masanin kimiyar Sweden Waldemar Jungner ya kirkira a shekarar 1899, an fi amfani da shi a cikin kananan na'urorin lantarki na wayar hannu, kamar masu tafiya da wuri, saboda yawan kuzarinsa fiye da batirin gubar-acid. Kama da baturan gubar-acid. Hakanan ana amfani da batura na nickel-cadmium tun cikin shekarun 1990s, amma yawan gubarsu yana da yawa, kuma baturin da kansa yana da takamaiman tasirin ƙwaƙwalwar ajiya. Wannan ne ma ya sa muke yawan jin wasu manya suna cewa sai an cire batirin gaba daya kafin a yi caji kuma batir na sharar gida zai gurbata kasa, da dai sauransu. (A lura cewa hatta batura na yanzu suna da guba sosai kuma bai kamata a jefar da su a ko'ina ba, amma batirin lithium na yanzu ba su da fa'idar ƙwaƙwalwar ajiya, kuma yawan fitar da wuta yana da illa ga rayuwar baturi.) Batirin Nickel-cadmium ya fi cutar da muhalli, kuma Su. Juriya na ciki zai canza tare da zafin jiki, wanda zai iya haifar da lalacewa saboda matsanancin halin yanzu yayin caji. Batirin nickel-hydrogen ya kawar da shi a hankali a kusa da 2005. Ya zuwa yanzu, ba a cika ganin batir nickel-cadmium a kasuwa ba.

Ma'aunin amsawar Electrode na baturin nickel-cadmium:

Positive electrode: 2NiO(OH)+2H_2 O+2e^-→2OH^-+2Ni〖(OH)〗_2

Negative electrode: Cd+2OH^-→Cd〖(OH)〗_2+2e^-

Lithium karfe baturi mataki

A cikin shekarun 1960, mutane a ƙarshe sun shiga zamanin batirin lithium a hukumance.

An gano karfen Lithium da kansa a shekara ta 1817, kuma ba da jimawa ba mutane suka gane cewa abubuwan da ake amfani da su na zahiri da sinadarai na lithium karfen su ana amfani da su azaman kayan batura. Yana da ƙananan yawa (0.534g 〖cm〗^(-3)), babban ƙarfin aiki (ka'idar har zuwa 3860mAh g ^ (-1)), da ƙarancin ƙarfinsa (-3.04V idan aka kwatanta da daidaitaccen lantarki na hydrogen). Waɗannan kusan suna gaya wa mutane ni ne kayan lantarki mara kyau na ingantaccen baturi. Koyaya, ƙarfen lithium kansa yana da manyan matsaloli. Yana da ƙarfi sosai, yana mai da martani da ruwa, kuma yana da manyan buƙatu akan yanayin aiki. Saboda haka, na dogon lokaci, mutane sun kasance marasa taimako da shi.

A cikin 1913, Lewis da Keyes sun auna yuwuwar lantarki na ƙarfe na lithium. Kuma gudanar da gwajin baturi tare da lithium iodide a cikin maganin propylamine a matsayin electrolyte, ko da yake ya kasa.

A cikin 1958, William Sidney Harris ya ambata a cikin karatun digirinsa cewa ya sanya ƙarfe na lithium a cikin hanyoyin ester na halitta daban-daban kuma ya lura da samuwar nau'ikan yadudduka na wucewa (ciki har da ƙarfe na lithium a cikin perchloric acid). Lithium LiClO_4

Abubuwan da ke faruwa a cikin maganin PC na propylene carbonate, kuma wannan bayani shine tsarin tsarin lantarki mai mahimmanci a cikin batura lithium a nan gaba), kuma an lura da wani takamaiman yanayin watsa ion, don haka an yi wasu gwaje-gwaje na farko na electrodeposition dangane da wannan. Waɗannan gwaje-gwajen a hukumance sun haifar da haɓaka batir lithium.

A cikin 1965, NASA ta gudanar da bincike mai zurfi kan caji da fitar da al'amura na Li||Cu baturi a cikin lithium perchlorate PC mafita. Sauran tsarin lantarki, gami da nazarin LiBF_4, LiI, LiAl〖Cl〗_4, LiCl.

A shekara ta 1969, wata takardar izini ta nuna cewa wani ya fara ƙoƙarin sayar da batir ɗin maganin kwayoyin halitta ta amfani da lithium, sodium, da potassium.

A cikin 1970, Kamfanin Panasonic na Japan ya ƙirƙira batirin Li‖CF_x┤, inda rabon x gabaɗaya 0.5-1. CF_x shine fluorocarbon. Ko da yake iskar fluorine yana da guba sosai, fluorocarbon kanta foda ce maras guba. Ana iya cewa fitowar batirin Li‖CF_x┤ shine baturin lithium na gaske na kasuwanci na farko. Li‖CF_x ┤ baturi babban baturi ne. Duk da haka, ƙarfin sa yana da girma, ƙarfin ka'idar shine 865mAh 〖Kg〗^(-1), kuma ƙarfin fitarwar sa yana da ƙarfi sosai a cikin dogon zango. Don haka, ƙarfin yana da ƙarfi kuma yanayin fitar da kai kaɗan ne. Amma yana da mummunan aiki kuma ba za a iya cajin shi ba. Saboda haka, gabaɗaya ana haɗa shi da manganese dioxide don yin batir Li‖CF_x ┤-MnO_2, waɗanda ake amfani da su azaman batir na ciki don wasu ƙananan firikwensin, agogo, da sauransu, kuma ba a kawar da su ba.

Na'urar lantarki mai inganci: CF_x+xe^-+x〖Li〗^+→C+xLiF

Wutar lantarki mara kyau: Li→〖Li〗^++e^-

A cikin 1975, Kamfanin Sanyo na Japan ya ƙirƙira batirin Li‖MnO_2┤, wanda aka fara amfani da shi a cikin na'urori masu cajin hasken rana. Ana iya ɗaukar wannan azaman baturin lithium na farko mai caji. Kodayake wannan samfurin ya kasance babban nasara a Japan a lokacin, mutane ba su da zurfin fahimtar irin wannan abu kuma ba su san lithium da manganese dioxide ba. Wane irin dalili ne ke bayan martanin?

Kusan a lokaci guda, Amurkawa suna neman batirin da za a sake amfani da shi, wanda a yanzu muke kira batirin sakandare.

A cikin 1972, MBArmand (sunayen wasu masana kimiyya ba a fassara su a farkon) an gabatar da su a cikin takardar taro M_(0.5) Fe 〖(CN)〗_3 (inda M shine ƙarfe alkali) da sauran kayan da tsarin shuɗi na Prussian. , Kuma yayi nazarin abubuwan da ke faruwa tsakanin ion ion. Kuma a cikin 1973, J. Broadhead da wasu na Bell Labs nazarin intercalation sabon abu na sulfur da aidin atom a karfe dichalcogenides. Waɗannan nazarce-nazarce na farko akan al'amarin ion intercalation sune mafi mahimmancin ƙarfin tuƙi don ci gaban batir lithium a hankali. Binciken na asali daidai ne saboda waɗannan binciken waɗanda batir lithium-ion daga baya suka zama mai yiwuwa.

A cikin 1975, Martin B. Dines na Exxon (wanda ya gabace Exxon Mobil) ya gudanar da ƙididdiga na farko da gwaje-gwaje a kan tsaka-tsakin tsaka-tsakin tsaka-tsakin tsaka-tsakin karfe dichalcogenides da ƙarfe alkali kuma a cikin wannan shekarar, Exxon wani suna Masanin Kimiyya MS Whittingham ya buga wani patent. akan Li‖TiS_2 ┤ pool. Kuma a cikin 1977, Exoon ya tallata baturi dangane da Li-Al‖TiS_2┤, wanda lithium aluminum gami zai iya inganta amincin baturin (ko da yake har yanzu akwai ƙarin haɗari). Bayan haka, irin waɗannan na'urorin batir sun yi amfani da su a jere ta Everready a Amurka. Kasuwancin Kamfanin Baturi da Kamfanin Grace. Batirin Li‖TiS_2 na iya zama baturin lithium na farko na farko a zahiri, kuma shi ne tsarin batir mafi zafi a lokacin. A lokacin, yawan kuzarinsa ya kai kusan sau 2-3 fiye da na batirin gubar-acid.

Kyakkyawan lantarki: TiS_2+xe^-+x〖Li〗^+→〖Li〗_x TiS_2

Wutar lantarki mara kyau: Li→〖Li〗^++e^-

A lokaci guda kuma, masanin kimiyyar Kanada MA Py ya ƙirƙira batirin Li‖MoS_2┤ a cikin 1983, wanda zai iya samun ƙarfin ƙarfin 60-65Wh 〖Kg〗^(-1) a 1/3C, wanda yayi daidai da Li‖TiS_2┤ baturi. Dangane da haka, a cikin 1987, kamfanin Moli Energy na Kanada ya ƙaddamar da batirin lithium na gaske wanda aka sayar da shi, wanda ake nema a duk duniya. Kamata ya yi wannan ya zama wani muhimmin lamari a tarihi, amma abin ban mamaki shi ne shi ma yana haifar da koma bayan Moli. Sannan a cikin bazara na 1989, Kamfanin Moli ya ƙaddamar da samfuran batirin Li‖MoS_2┤ ƙarni na biyu. A ƙarshen bazara na 1989, samfurin baturi na farko na Moli Li‖MoS_2┤ ya fashe kuma ya haifar da firgici mai girma. A lokacin rani na wannan shekarar, an tuna da duk samfuran, kuma an biya wa waɗanda abin ya shafa diyya. A karshen wannan shekarar, Moli Energy ya bayyana fatarar kudi kuma hukumar NEC ta Japan ta samu a cikin bazara na 1990. Ya kamata a ambata cewa an yi ta rade-radin cewa Jeff Dahn, wani masanin kimiyar Kanada a lokacin, shi ne ya jagoranci aikin batir a Moli. Makamashi kuma yayi murabus saboda adawarsa da ci gaba da jerin batir Li‖MoS_2┤.

Kyakkyawan lantarki: MoS_2+xe^-+x〖Li〗^+→〖Li〗_x MoS_2

Wutar lantarki mara kyau: Li→〖Li〗^++e^-

Ya zuwa yanzu, batirin karfen lithium sannu a hankali ya bar idon jama'a. Za mu iya ganin cewa a cikin lokacin daga 1970 zuwa 1980, binciken masana kimiyya akan baturan lithium ya fi mayar da hankali kan kayan cathode. Burin ƙarshe yana mai da hankali koyaushe akan ƙarfe dichalcogenides na canji. Saboda tsarin da suke da shi (transition karfe dichalcogenides yanzu ana nazarin ko'ina a matsayin abu mai nau'i biyu), yadudduka kuma Akwai isassun gibi tsakanin yadudduka don ɗaukar shigar da ion lithium. A wancan lokacin, an sami ɗan bincike kan kayan anode a wannan lokacin. Ko da yake wasu nazarin sun mayar da hankali ne kan haɗakar da ƙarfen lithium don haɓaka kwanciyar hankali, ƙarfen lithium da kansa ba shi da ƙarfi kuma yana da haɗari. Ko da yake fashewar batir Moli al'amari ne da ya girgiza duniya, an sha samun Alkawura da dama na fashewar baturan karfen lithium.

Haka kuma, mutane ba su san musabbabin fashewar batir lithium da kyau ba. Bugu da kari, an taba daukar karfen lithium a matsayin wani abu mara kyau na lantarki saboda kyawawan kaddarorinsa. Bayan fashewar batirin Moli, karbuwar da mutane suka yi da batirin karfen lithium ya ragu matuka, kuma batirin lithium ya shiga wani lokaci mai duhu.

Don samun ingantaccen baturi, dole ne mutane su fara da kayan lantarki mai cutarwa. Duk da haka, akwai jerin matsaloli a nan: yuwuwar yuwuwar ƙarfe na lithium ba shi da zurfi, kuma yin amfani da sauran gurɓatattun na'urorin lantarki zai ƙara ƙarfin ƙarfin lantarki mara kyau, kuma ta wannan hanyar, batirin lithium Bambanci gaba ɗaya zai ragu, wanda zai rage. yawan makamashi na hadari. Saboda haka, masana kimiyya dole ne su nemo daidai high-voltage cathode abu. A lokaci guda, wutar lantarki na baturi dole ne ya dace da ingantacciyar wutar lantarki da mara kyau da kwanciyar hankali. A lokaci guda, da conductivity na electrolyte Kuma zafi juriya ne mafi alhẽri. Wannan jerin tambayoyin sun daɗe da ruɗar masana kimiyya don samun ƙarin gamsasshiyar amsa.

Matsala ta farko da masana kimiyya za su magance ita ce samun lafiyayyen abu mai cutarwa na lantarki wanda zai iya maye gurbin karfen lithium. Lithium karfe da kansa yana da aikin sinadarai da yawa, kuma jerin matsalolin ci gaban dendrite sun kasance masu tsauri akan yanayin amfani da yanayin, kuma ba shi da aminci. Graphite yanzu shine babban jikin mummunan electrode na batirin lithium-ion, kuma an yi nazarin aikace-aikacen sa a cikin batir lithium tun a farkon 1976. A cikin 1976, Besenhard, JO ya gudanar da ƙarin cikakken bincike game da haɗin gwiwar electrochemical na LiC_R. Duk da haka, kodayake graphite yana da kyawawan kaddarorin (high conductivity, high power, low m, inertness, da dai sauransu), a lokacin, da electrolyte amfani a lithium baturi ne kullum PC bayani na LiClO_4 da aka ambata a sama. Graphite yana da matsala mai mahimmanci. Idan babu kariyar, ƙwayoyin cuta na PC ɗin lantarki suma za su shiga tsarin graphite tare da haɗin gwiwar lithium-ion, wanda ke haifar da raguwar aikin sake zagayowar. Saboda haka, graphite ba su da fifiko ga masana kimiyya a lokacin.

Dangane da kayan cathode, bayan binciken matakin baturi na ƙarfe na lithium, masana kimiyya sun gano cewa kayan lithium anode da kansa shima kayan ajiyar lithium ne tare da juzu'i mai kyau, kamar LiTiS_2, ''Li〗_x V〖Se〗_2 (x) = 1,2) da sauransu, kuma a kan wannan, an ƙera 〖Li〗_x V_2 O_5 (0.35≤x<3), LiV_2 O_8 da sauran kayan. Kuma a hankali masana kimiyya sun saba da tashoshi 1-dimensional ion tashoshi (1D), 2-dimensional layered ion intercalation (2D), da kuma tsarin sadarwa na watsawa mai girma 3.

Shahararren binciken Farfesa John B. Goodenough akan LiCoO_2 (LCO) shima ya faru a wannan lokacin. A cikin 1979, Goodenougd et al. An yi wahayi zuwa ga labarin kan tsarin NaCoO_2 a cikin 1973 kuma an gano LCO kuma ya buga labarin haƙƙin mallaka. LCO yana da tsarin tsaka-tsakin tsaka-tsaki mai kama da canjin ƙarfe disulfides, wanda za'a iya sake saka ions lithium da fitar da su. Idan an fitar da ion lithium gaba daya, za a samar da tsarin CoO_2 na kusa, kuma za a iya sake shigar da shi tare da ions lithium don lithium (Hakika, ainihin baturi ba zai bari a fitar da ions na lithium gaba daya ba, wanda hakan zai haifar da ci gaba. zai sa karfin ya lalace da sauri). A cikin 1986, Akira Yoshino, wanda har yanzu yana aiki a Kamfanin Asahi Kasei a Japan, ya haɗu da uku na LCO, Coke, da LiClO_4 PC bayani a karon farko, ya zama baturi na biyu na lithium-ion na zamani kuma ya zama lithium na yanzu. baturi. Sony da sauri ya lura da "mai kyau isa" ikon mallakar LCO na tsohon mutum kuma ya sami izini don amfani da shi. A cikin 1991, ya tallata batirin lithium-ion LCO. Tunanin batirin lithium-ion shima ya bayyana a wannan lokacin, kuma ra'ayinsa Har ila yau yana ci gaba har zuwa yau. (Yana da mahimmanci a lura cewa batir lithium-ion na farko na Sony da Akira Yoshino suma suna amfani da carbon mai ƙarfi azaman gurɓataccen lantarki maimakon graphite, kuma dalilin shine PC ɗin da ke sama yana da haɗin gwiwa a cikin graphite)

Kyakkyawan lantarki: 6C+xe^-+x〖Li〗^+→〖Li〗_x C_6

Wutar lantarki mara kyau: LiCoO_2→〖Li〗_(1-x) CoO_2+x〖Li〗^++xe^-

A daya hannun, a cikin 1978, Armand, M. ya ba da shawarar yin amfani da polyethylene glycol (PEO) a matsayin m polymer electrolyte don warware matsalar a sama cewa graphite anode ne sauƙin saka a cikin sauran ƙarfi PC kwayoyin (mafi yawan electrolyte a wancan lokacin har yanzu. yana amfani da PC, DEC gaurayawan bayani), wanda ya sanya graphite a cikin tsarin baturi na lithium a karon farko, kuma ya ba da shawarar manufar baturin kujeru (rocking-chair) a cikin shekara mai zuwa. Irin wannan ra'ayi ya ci gaba har zuwa yanzu. Na'urorin lantarki na yau da kullun, kamar ED/DEC, EC/DMC, da sauransu, a hankali sun bayyana a cikin 1990s kuma ana amfani dasu tun daga lokacin.

A daidai wannan lokacin, masana kimiyya sun kuma bincika jerin batura: Li‖Nb〖Se〗_3 ┤ baturi, Li‖V〖SE〗_2 ┤ baturi, Li‖〖Ag〗_2 V_4 ┤ O_11 baturi, Li․ Baturi. Li ‖I_2 ┤Batura, da dai sauransu, saboda ba su da kima a yanzu, kuma babu nau'ikan bincike da yawa don kada in gabatar da su dalla-dalla.

• Batirin Li-ion mataki

Zamanin haɓaka batirin lithium-ion bayan 1991 shine zamanin da muke ciki yanzu. Anan ba zan taƙaita tsarin ci gaban dalla-dalla ba amma a taƙaice gabatar da tsarin sinadarai na batir lithium-ion kaɗan.

Gabatarwa ga tsarin batirin lithium-ion na yanzu, ga sashi na gaba.