Iyo cathode zvinhu ndiyo yekutanga sosi ye lithium ions mu alithium-ion bhatiri. Panguva yekuchaja, lithium ions inotorwa kubva kune cathode material's crystal lattice uye kupinda mune anode zvinhu; reverse inoitika panguva yekubuda. Kugona kudzorereka uye voltage plateau ye cathode material panguva yekuchaja nekuburitsa zvinonyanya kuratidza kusimba kwebhatiri relithium-ion. Uyezve, nekuti iyo cathode material ine simbi dzakaita selithium, cobalt, uye nickel, inoumba chikamu chakakosha chemutengo welithium -ion bhatiri.
Kugadzira zvinhu zvecathode zvine simba rakanyanya density, yakakwira inobuda voltage, hupenyu hurefu hwesevhisi, uye kureruka kwekugadzira kwakakosha zvikuru. Yakanaka cathode zvinhu inofanira kusangana neanotevera mamiriro ezvinhu.
(1) Iine yakakwira redox inogoneka, ichivimbisa yakakwira yekubuda voltage yebhatiri.
(2) Inogona kugarisa akawanda lithium ions sezvinobvira, kuve nechokwadi chepamusoro bhatiri huwandu.
(3) Panguva yekuiswa uye kubudiswa kwe lithium ions, iyo cathode zvinhu inogona kuchengetedza kugadzikana kwayo kwemaitiro, nokudaro kuve nechokwadi chehupenyu hurefu hwekutenderera kwe electrode.
(4) Iine yakanakisa yemagetsi uye ion conductivity, inonyatso kudzikisa kurasikirwa kwesimba kunokonzerwa nepolarization mhedzisiro, nekudaro ichivimbisa kukurumidza kuchaja uye kugona kubuda kwebhatiri.
(5) Kushanda kwebhatiri kwemagetsi kunofanirwa kunge kuri mukati meiyo electrochemical kugadzikana kweiyo electrolyte, nekudaro ichidzikisa kusingakoshi kwemakemikari kuita pakati pemagetsi emagetsi ne electrolyte.
(6) Haingofanire kunge iine mutengo wakaderera uye yakapusa synthesis process, asi inofanirawo kuratidza hushamwari hwepamusoro kwezvakatipoteredza.
Uyezve, iyo cathode zvinhu inofanirawo kuratidza yakanakisa electrochemical uye kugadzikana kwekupisa.
Zvishandiso zviripo zvecathode zvinogona kunyanya kukamurwa kuita zvikamu zvitatu zvichienderana nekusiyana kwechimiro chekristaro: ① dhizaini, se lithium cobalt oxide (LiCoO2) uye ternary zvinhu (LiNiCo, Mni-x-yO2); ② chimiro che olivine, yakadai se lithium iron phosphate (LiFePO4); ③ spinel structure oxides, zvakadai se lithium manganese oxide (LiMn2O4) uye lithium nickel manganese oxide (LiNi10.5Mn1.5O4). Mhando dzakasiyana dzekathodhi dzine akasiyana simba density, electrochemical hunhu, uye mutengo, pakupedzisira uchiita kuti ive yakakodzera kune akasiyana minda uye mamiriro ekushandisa. Layered structure cathode materials inoreva cathode zvinhu zvine layered microcrystalline structure, kunyanya kusanganisira lithium cobalt oxide, lithium nickel cobalt manganese oxide, uye lithium{12}rich manganese oxide. Pakati pawo, lithium cobalt oxide nelithium nickel cobalt manganese oxide parizvino ndiwo ari kunyanya kushandiswa zvakanyanya necathode zvinhu zvelithium-mabhatiri eion muzvigadzirwa zvemagetsi edhijitari uye simba relithium{15}}mabhatiri eion. Iwo anoratidzirwa nekuwanda kwesimba, kuita kwakanakisa kutenderera, uye kuita kwakanaka kwese, asi chikamu chepamusoro chesimbi senge nickel, cobalt, uye manganese inotungamira kumitengo yakakwira.
Lithium cobalt oxide cathode zvinhu
Lithium cobalt oxide (LiCoO2) yakawanikwa nemusayendisiti wekuAmerica uye mubairo weNobel muChemistry, JB Goodenough, uye yakatanga kutengeswa neSony Corporation yekuJapan muma1990s. Kunyangwe nanhasi, lithium cobalt oxide inoramba iri imwe yemidziyo yecathode ine yakanyanya volumetric simba density. Nechikonzero ichi, inoshandiswa zvakanyanya mudhijitari pouch cell zvigadzirwa zvinoda yakakwira volumetric simba density, senge nharembozha, smartwatches, uye Bluetooth mahedhifoni.
Lithium cobalt oxide (LiCoO2), as one of the earliest commercially available cathode materials, possesses a volumetric energy density unmatched by other cathode materials. Electrodes prepared from LiCoO2 can achieve a compaction density exceeding 4.2 g/cm², and a specific capacity of 185 mA·h/g at high voltage (>4.45V). Pamusoro pezvo, LiCoO2 inotaridza kufambiswa zvakanaka kwemagetsi neayoni, kushanda nesimba kwesimba, uye -kuchaja zvinhu zvinokurumidza, zvichizadzisa zvinodiwa nemabhatiri emagetsi evatengi vemazuva ano nekudaro kuva nemaapplication akawanda. Kubva pane izvi zvivakwa, LiCoO2 inoramba iri imwe yeakanakisa cathode zvinhu kusvika parizvino.
Nzira huru dzekugadzira lithium cobalt oxide dzinosanganisira yakakwirira-tembiricha yakasimba-state synthesis, sol-gel synthesis, uye yakaderera{3}}kupindwa kwematembiricha. Kuwedzera-tembiricha yakasimba-kusanganiswa kwemamiriro ekunze kunosanganisira kusanganisa munyu welithium necobalt{7}}ine maokisidesi kana mahydroxides mune imwe stoichiometric reshiyo, wozoita calcining musanganiswa patembiricha yakakodzera kwenguva yakati, zvichiteverwa nekutonhodza, kupuruzira, nekusefa kuti uwane sampuli. Kunyange zvazvo iyo-tembiricha yakasimba-ino shandiswa zvakanyanya mukugadzirwa kwemaindasitiri, inotora nguva{11}}, inoda tembiricha yepamusoro, uye inogadzira poda hombe, isina kuenzana ine homogeneous ine misiyano ye stoichiometric, zvichiita kuti mutengo uwedzere.
Phosphate cathode zvinhu
Muna 1997, Goodenough et al. yakatanga kukurudzirwa lithium iron phosphate (LiFePO4) sechinhu checathode chelithium-mabhatiri eion.
Nekuda kwekudhura kwayo, chimiro chakasimba, uye kuchengetedzwa kwepamusoro, chinhu ichi chave zvishoma nezvishoma chimwe chezvinhu zvinofarirwa zvecathode zvelithium-mabhatiri eion mumabhazi emagetsi uye masisitimu ekuchengetedza simba.
Lithium iron phosphate (LiFePO4) inogovera chimiro chekristal chakafanana uye crystal system ine iron phosphate (FePO4). Izvi zvinoreva kuti zvinhu zvinowana shanduko shoma yevhoriyamu panguva yelithium-ion yekuisa/kubvisa, zvichidzivirira kukuvadzwa kwelatisi kunokonzerwa nekuwedzera vhoriyamu kana kudhonzwa. Uyezve, hunhu uhwu hunovimbisa kubatana kwakanaka kwemagetsi pakati pezvimedu uye conductive additives, zvichikonzera kugadzikana kwekutenderera uye hupenyu hurefu. Pamusoro pezvo, lithium iron phosphate inozivikanwa nekusagadzikana kwezvakatipoteredza, mutengo-kushanda zvakanaka, kuchengetedzeka kwakanakisa, huwandu hwepamusoro (inoda kusvika 170 mA·h/g), uye chikuva chakatsiga chekuchaja/kuburitsa. Tichifunga zvakanakira izvi, lithium iron phosphate inoonekwa seyakanakisa sarudzo yemidziyo yecathode muhukuru-mashandisirwo ekuchengetedza simba.
Nzira idzi dzinosanganisira sol-gel process, coprecipitation techniques, uye hydrothermal synthesis. Kunyanya, hydrothermal synthesis inogadzira yakananga chigadzirwa mune autoclave nekuwedzera tembiricha uye kudzvanywa, uchishandisa inowanikwa zviri nyore iron, lithium, uye phosphorus makomisheni seyakagadzirwa zvinhu. Iyi nzira inozivikanwa nekushanda kwayo kuri nyore, diki uye yunifomu particle size, uye kuderera kwesimba rekushandisa. Zvisineyi, ine painogumira pakugadzirwa kwemaindasitiri, zvakanyanya nekuda kwekudiwa kwezvigadziro zvakagadzirirwa zvakasimba-zvinoshingirira. Coprecipitation, kune rumwe rutivi, inoitwa mune yemhinduro sisitimu, uko precursor morphology inobatwa nezvinhu zvakasiyana senge kusungirira, tembiricha kutonga, pH kugadziridzwa, uye kumhanyisa mwero. Tichifunga nezve basa rinoita maparamendi aya mukuita kwekupedzisira sintered LiFePO zvinhu, kunyatsosarudzwa kwemamiriro ekuyedza kwakakosha. Zvigadzirwa zvakagadzirirwa neiyi nzira hazvingove neakanakisa microstructure maitiro (kureva, diki uye yunifomu saizi) asiwo anoratidza epamusoro electrochemical zvimiro; zvisinei, zvakakosha kuziva kuti hurongwa hwese hwekushanda hwakaoma, uye matambudziko ekusefa uye nyaya dzekugadzirisa tsvina dzinogona kubuda panguva yekugadzirisa.
Lithium manganese oxide uye lithium{{0}rich manganese{1}based cathode materials
Lithium manganese oxide
Mukutsvagisa zvinhu zvelithium-ion bhatiri cathode zvinhu, chimwe chinhu chakakosha uye chinowanika mukutengesa chinonzi spinel{1}}structured lithium manganese oxide (LiMn₂O₄) cathode material yakakurudzirwa naThackeray et al. muna 1983. Spinel{4}structured lithium manganese oxide ndeye cubic crystal system. Yayo yakajairika makemikari kuumbwa LiMn₂O₄. MuLiMn₂O₄ crystal structure, okisijeni iri kumeso-centered cubic close{8}}packed structure, ukuwo manganese neoxygen zvinoumba octahedral structure, sezviri kuratidzwa pamufananidzo uri pazasi.
Manganese yakawandisa pachisikirwo, uye magadzirirwo espinel-type lithium manganese oxide (LiMn2O4) anoratidza maitiro akasiyana. Iyo synthesis nzira uye yekugadzira tekinoroji yezvinyorwa inokanganisa zvakananga iyo microstructure uye zviyo kukura kwechigadzirwa chekupedzisira. Naizvozvo, kukwenenzvera aya masisitimu maitiro kwakakosha pakuvandudza mashandiro emagetsi emagetsi emagetsi mukushandisa. Parizvino, indasitiri nedzidzo dzinoshandisa nzira mbiri huru dzekugadzira LiMn2O4: imwe yakavakirwa pakudyidzana kuri pakati pezvinhu zvakasimba, zvakaita seyepamusoro-tembiricha yakasimba-maitikiro emamiriro ezvinhu, microwave{10}assisted synthesis, uye kurapwa kwekuisa pamuviri mune zvakanyungudutswa munyu.
Chimwe chikamu chinosanganisira kusandurwa kwemakemikari munzvimbo ine mvura, ine mimwe mienzaniso inosanganisira sol-gel tekinoroji, hydrothermal synthesis, uye coprecipitation maitiro. LiMnzO4 yakwezva kutarisisa kwakapararira nekuda kwemutengo wayo mukana, yakanakisa kugadzikana kwemafuta, kuramba kwakasimba kwechaji, uye yakanaka mabhenefiti ezvakatipoteredza. Nekudaro, chinyorwa ichi chine zvikanganiso mukuchovha bhasikoro uye kuita kwekuchengetedza, kunyanya pakupisa kwakanyanya, uko kuita kwayo bhasikoro kunodzikira zvakanyanya, zvichikonzera kurasikirwa kwesimba kusingadzoreki.
lithium{{0}rich manganese-based
Kunze kwelithium manganese oxide, rakaiswa lithium{{0}yakapfuma manganese{1}yakabva yakwezva kutarisisa kwakapararira sechinhu chiri kubuda checathode yelithium{2}}mabhatiri eion.
Nzira dzekugadzirira dzelithium{{0}rich manganese{{1}based cathode materials dzinosanganisira solid-state ways, sol-gel nzira, uye co-nzira dzekunaya. Nzira yakasimba-yenyika inosanganisira kusanganisa zvakananga metal oxides nesimbi carbonates kana metal hydroxides mune imwe chikamu, ichiteverwa nepamusoro-tembiricha yakasimba-state reaction to get layered lithium{9}}zvakapfuma. Zvakanakira-nyika nzira kugona kwayo kugadzira yakawanda yakawanda yelayered lithium{12}}zvakapfuma, nzira yayo yekugadzirira iri nyore, uye mutengo wayo wakaderera. Zvakaipa kusakosha kweiyo solid diffusion coefficient of solid panguva-state sintering, uye nyaya yekuti masimbi akasiyana ane diffusion rates mune{15}}state reaction yakasimba, zvichiita kuti zviome kuti zvimedu zvipararire zvakakwana. Nokudaro, kufanana kwezvinhu zvakagadzirwa hazvina kunaka, izvo zvinokanganisa kushanda kwekathode zvinhu. Iyo sol-gel nzira inosanganisira kutanga yaisa shanduko yesimbi munyu musanganiswa kuti iite sol, yobva yapfavisa mvura kuti iite gel, uye pakupedzisira kuiomesa nekukanika kuti iwane yakaturikidzana lithium{19}}zvakapfuma. Iyi nzira inobereka zvinhu zvine yunifomu yekugovera uye kuchena kwakanyanya, uye ma electrode anogadzirwa anoratidza kuita kwakanaka kwe electrochemical. Zvisinei, zvipingamupinyi zvayo zvinosanganisira kutenderera kwenguva refu kwekugadzira, kudiwa kwevakawanda vanobatanidza (organic acids kana ethylene glycol), zvichiita kuti mari iwedzere. Zvakare, iyo yakaturikidzana yelithium-yakapfuma zvinhu zvinonyanya kunaka nano/micron zvimedu zvine kuderera chaiko. Naizvozvo, nzira iyi parizvino inonyanya kushandiswa mumarabhoritari kugadzira lithium yakaturikidzana-yakapfuma uye inonetsa kuitengesa.
Yepamusoro-nickel cathode zvinhu
Vatsvakurudzi vakatsvaga kwenguva yakareba-kugadzikana kwematembiricha uye kushanda zvakanaka kwechiyero sezvinangwa zvekutanga pakugadzira cathode.
zvinhu zvemabhatiri e lithium-ion. Pakati pezvinhu zvitatu zvikuru - LiCoO₂, LiNi₁ₓ₋ᵧCoₓMnᵧO₂ (NCM), uye LiFePO₄ - NCM inoonekwa seimwe yezvinhu zvinonyanya kuvimbiswa zvecathode nekuda kwehukuru hwayo hwepamusoro, mutengo wakaderera wemidziyo, mutengo wepamusoro weLife uye kuchengetedzwa kwenzvimbo zvinhu.
Rudzi urwu rwezvinhu rune zvakafanana {-NaFeO₂-mhando yakaturikidzana sekristaro chimiro uye ndecheR-3m space group. Iyi pfungwa yakatanga kutaurwa naLiu et al. mu 1999. Inobatanidza noungwaru zvakanakira zvinhu zvitatu zvecathode - lithium cobalt oxide (LiCoO₂), lithium nickel oxide (LiNiO₂), uye lithium manganese oxide (LiMnO₂) - uye inogadzirisa zvinobudirira kukanganisa kunowanikwa mune imwe neimwe nyaya (sezvinoratidzwa muFigure 5-6). Nekugadzirisa chiyero cheshanduko yesimbi zvinhu, iyo yakakwana chiyero pakati pehumwe hunyanzvi, kuita kutenderera, kuchengetedza, uye mutengo unogona kuwanikwa zvakare.
Iyo crystal chimiro chelithium nickel cobalt manganese oxide (NCM) ternary cathode zvinhu zvakangofanana neiyo yeLiCoO2, ese ari eiyo hexagonal akaturikidzana chimiro.
