E hiki mai ana ka hooilo, e nana i ke ano haahaa haahaa ana o na paani lithium-ion

Hoʻopilikia nui ʻia ka hana o nā pā lithium-ion e ko lākou mau hiʻohiʻona kinetic. No ka mea, pono e hoʻopau mua ʻia ʻo Li+ ke hoʻokomo ʻia i loko o ka mea graphite, pono ia e ʻai i kekahi nui o ka ikehu a keʻakeʻa i ka laha ʻana o Li+ i loko o ka graphite. ʻO ka mea ʻē aʻe, ke hoʻokuʻu ʻia ʻo Li + mai ka mea graphite i ka hopena, e hana mua ke kaʻina hana hoʻonā, a ʻaʻole pono ke kaʻina hoʻonā i ka ikehu. Hiki iā Li+ ke hoʻoneʻe koke i ka graphite, e alakaʻi ana i ka ʻae ʻana i ka uku ʻilihune o ka mea graphite. I ka hoʻokuʻu ʻana i ka ʻae ʻia.

I nā haʻahaʻa haʻahaʻa, ua hoʻomaikaʻi a ʻoi aku ka maikaʻi o nā ʻano kinetic o ka electrode graphite maikaʻi ʻole. No laila, ua hoʻoikaika nui ʻia ka polarization electrochemical o ka electrode maikaʻi ʻole i ka wā o ke kaʻina hana, hiki ke alakaʻi maʻalahi i ka ua o ka lithium metallic ma ka ʻili o ka electrode maikaʻi ʻole. Ua hōʻike ʻia ka noiʻi a Christian von Lüders o ke Kulanui ʻenehana o Munich, Kelemānia, ma -2 ° C, ʻoi aku ka nui o ka uku ma mua o C/2, a ua hoʻonui nui ʻia ka nui o ka ua metala lithium. No ka laʻana, ma ka helu C/2, ʻo ka nui o ka lithium plating ma ka ʻaoʻao electrode kū'ē e pili ana i ka uku holoʻokoʻa. 5.5% o ka mana akā hiki i ka 9% ma lalo o 1C hoʻonui. Hiki ke ulu hou ka lithium metallic precipitated a lilo i lithium dendrites, e hou ana ma ka diaphragm a hoʻopōkole i nā electrodes maikaʻi a maikaʻi ʻole. No laila, pono e pale i ka hoʻouka ʻana i ka pā lithium-ion i nā haʻahaʻa haʻahaʻa e like me ka hiki. I ka wā e pono ai e hoʻopaʻa i ka pākaukau ma kahi haʻahaʻa haʻahaʻa, pono ia e koho i kahi manawa liʻiliʻi e hoʻopiʻi i ka pā lithium-ion e like me ka hiki a mālama pono i ka pā lithium-ion ma hope o ka hoʻopaʻa ʻana e hōʻoia ʻO ka lithium metallic precipitated mai ka electrode maikaʻi ʻole. hiki ke hana me ka graphite a hoʻokomo hou i loko o ka electrode graphite maikaʻi ʻole.

Ua hoʻohana ʻo Veronika Zinth a me nā mea ʻē aʻe o ke Kulanui ʻenehana o Munich i ka diffraction neutron a me nā ʻano hana ʻē aʻe e aʻo ai i ka ʻano hoʻololi lithium o nā pā lithium-ion ma kahi haʻahaʻa haʻahaʻa o -20°C. ʻO ka neutron diffraction kahi ala ʻike hou i nā makahiki i hala iho nei. Ke hoʻohālikelike ʻia me XRD, ʻoi aku ka maʻalahi o ka neutron diffraction i nā mea māmā (Li, O, N, etc.), no laila ua kūpono loa ia no ka hoʻāʻo ʻole ʻana i nā pā lithium-ion.

I loko o ka hoʻokolohua, hoʻohana ʻo VeronikaZinth i ka pākaukau NMC111/graphite 18650 e aʻo i ka ʻano hoʻololi lithium o nā pā lithium-ion ma nā haʻahaʻa haʻahaʻa. Hoʻopiʻi ʻia ka pākaukau a hoʻokuʻu ʻia i ka wā o ka hoʻāʻo e like me ke kaʻina hana i hōʻike ʻia ma ke kiʻi ma lalo nei.

Hōʻike kēia kiʻi i ka hoʻololi ʻana o ka electrode maikaʻi ʻole ma lalo o nā SoC ʻokoʻa i ka wā o ka lua o ka hoʻouka ʻana ma ka C/30 rate charging. Me he mea lā ma ka 30.9% SoC, ʻo nā pae o ka electrode maikaʻi ʻole ka nui o LiC12, Li1-XC18, a me kahi liʻiliʻi o LiC6 Composition; ma hope o ka SoC ma mua o 46%, hoʻomau ka emi ʻana o ka diffraction intensity o LiC12, ʻoiai ke hoʻomau nei ka mana o LiC6. Eia nō naʻe, ʻoiai ma hope o ka pau ʻana o ka hoʻopiʻi hope, ʻoiai ʻo 1503mAh wale nō i hoʻopiʻi ʻia i ka haʻahaʻa haʻahaʻa (ʻo 1950mAh ka mana ma ka lumi wela), aia ʻo LiC12 i ka electrode maikaʻi ʻole. Manaʻo e hoʻemi ʻia ke au o ka hoʻouka ʻana i C/100. I kēlā hihia, hiki i ka pākaukau ke loaʻa i ka mana o 1950mAh ma nā haʻahaʻa haʻahaʻa, e hōʻike ana i ka emi ʻana o ka mana o nā pā lithium-ion i nā haʻahaʻa haʻahaʻa ma muli o ka emi ʻana o nā kūlana kinetic.

Hōʻike ka kiʻi ma lalo i ka hoʻololi ʻana o ka graphite i ka electrode maikaʻi ʻole i ka wā o ka hoʻouka ʻana e like me ka helu C/5 ma kahi haʻahaʻa haʻahaʻa o -20°C. Hiki iā ia ke ʻike he ʻokoʻa loa ka hoʻololi ʻana o ka pae o ka graphite i ka hoʻohālikelike ʻana i ka C/30 rate charging. Hiki ke ʻike ʻia mai ke kiʻi i ka wā o SoC>40%, ʻoi aku ka lohi o ka pae ikaika o ka pākaukau LiC12 ma lalo o ka C/5 charge rate, a ʻoi aku ka nāwaliwali o ka piʻi ʻana o ka LiC6 phase ikaika ma mua o ka C/30. uku uku. Hōʻike ia ma kahi kiʻekiʻe kiʻekiʻe o C/5, liʻiliʻi ka LiC12 e hoʻomau i ka intercalate lithium a hoʻololi ʻia i LiC6.

Hoʻohālikelike ka kiʻi ma lalo nei i nā hoʻololi ʻana o ka electrode graphite maikaʻi ʻole i ka wā e hoʻopiʻi ana ma nā helu C/30 a me C/5. Hōʻike ke kiʻi no ʻelua mau uku hoʻopiʻi like ʻole, ʻano like ka lithium-poor phase Li1-XC18. Hōʻike nui ʻia ka ʻokoʻa i nā ʻāpana ʻelua o LiC12 a me LiC6. Hiki ke ʻike ʻia ma ke kiʻi e pili kokoke ana ke ʻano hoʻololi o ka pae i ka electrode maikaʻi ʻole i ka pae mua o ka hoʻouka ʻana ma lalo o nā uku uku ʻelua. No ka pae LiC12, i ka hiki ʻana o ka mana hoʻopiʻi i 950mAh (49% SoC), hoʻomaka ka ʻano loli. I ka hiki ʻana mai o 1100mAh (56.4% SoC), hoʻomaka ka LiC12 ma lalo o nā hoʻonui ʻelua e hōʻike i kahi āpau koʻikoʻi. I ka hoʻoukaʻana i kahi haʻahaʻa haʻahaʻa o C / 30, wikiwiki loa ka emiʻana o ka pae LiC12, akā,ʻoi aku ka lohi o ka hāʻule o ka LiC12 ma ka C / 5; ʻo ia hoʻi, ʻoi aku ka maikaʻi o nā kūlana kinetic o ka hoʻokomo ʻana o ka lithium i ka electrode maikaʻi ʻole i nā haʻahaʻa haʻahaʻa. , No laila e hoʻopili hou ai ʻo LiC12 i ka lithium e hoʻohua i ka wikiwiki o ka pae LiC6 i hoʻemi ʻia. Pēlā nō, piʻi wikiwiki ka pae LiC6 ma kahi haʻahaʻa haʻahaʻa o C/30 akā ʻoi aku ka lohi ma kahi pākēneka o C/5. Hōʻike kēia i ka helu C/5, ʻoi aku ka liʻiliʻi liʻiliʻi liʻiliʻi liʻiliʻi i hoʻokomo ʻia i loko o ka ʻano aniani o ka graphite, akā ʻo ka mea hoihoi, ʻoi aku ka kiʻekiʻe o ka mana o ka pākaukau (1520.5mAh) ma ka helu C/5 ma mua o ka C /30 uku uku. ʻOi aku ka mana (1503.5mAh). ʻO ka Li hou ʻaʻole i hoʻokomo ʻia i loko o ka electrode graphite maikaʻi ʻole e hoʻoheheʻe ʻia ma ka ʻili graphite ma ke ʻano o ka lithium metala. ʻO ke kaʻina hana kū ma hope o ka pau ʻana o ka hoʻopiʻi ʻana e hōʻoiaʻiʻo ana i kēia mai ka ʻaoʻao - liʻiliʻi.

Hōʻike ke kiʻi ma lalo nei i ke ʻano o ka hana o ka electrode graphite maikaʻi ʻole ma hope o ka hoʻouka ʻana a ma hope o ka waiho ʻana no 20 mau hola. I ka pau ʻana o ka hoʻopiʻi ʻana, ʻokoʻa loa ka māhele o ka electrode graphite maikaʻi ʻole ma lalo o nā uku hoʻoili ʻelua. Ma C / 5, ʻoi aku ka kiʻekiʻe o ka lākiō o LiC12 i ka anode graphite, a ʻoi aku ka haʻahaʻa o ka LiC6, akā ma hope o ke kū ʻana no 20 mau hola, ua liʻiliʻi ka ʻokoʻa ma waena o nā mea ʻelua.

Hōʻike ke kiʻi ma lalo nei i ka hoʻololi ʻana o ka electrode graphite maikaʻi ʻole i ka wā o ke kaʻina mālama 20h. Hiki iā ia ke ʻike mai ke kiʻi ʻoiai he ʻokoʻa loa nā pae o nā electrodes kū'ē ʻelua i ka hoʻomaka ʻana, i ka piʻi ʻana o ka manawa mālama, nā ʻano ʻelua o ka hoʻouka ʻana Ua loli kokoke loa ke kahua o ka anode graphite ma lalo o ka hoʻonui. Hiki ke hoʻomau i ka hoʻololi ʻana i LiC12 i LiC6 i ka wā o ke kaʻina hana shelving, e hōʻike ana e hoʻomau ʻia ʻo Li i ka graphite i ka wā o ke kaʻina hana shelving. ʻO kēia ʻāpana o Li paha he lithium metala i hoʻoheheʻe ʻia i ka ʻili o ka electrode graphite maikaʻi ʻole ma ka wela haʻahaʻa. Ua hōʻike hou ʻia ka nānā ʻana i ka hopena o ka hoʻopiʻi ʻana ma ka helu C/30, ʻo ke degere o ka intercalation lithium o ka electrode graphite maikaʻi ʻole he 68%. Eia nō naʻe, piʻi ka pae o ka intercalation lithium i 71% ma hope o ka mālama ʻana, kahi piʻi o 3%. I ka pau ʻana o ka hoʻopiʻi ʻana ma ka helu C / 5, ʻo ka lithium insertion degree o ka electrode graphite maikaʻi ʻole he 58%, akā ma hope o ka waiho ʻia ʻana no nā hola 20, ua hoʻonui ʻia i 70%, ka piʻi nui o 12%.

Hōʻike ka noiʻi ma luna nei i ka wā e hoʻopiʻi ai i nā haʻahaʻa haʻahaʻa, e emi ana ka nui o ka pākaukau ma muli o ka emi ʻana o nā kūlana kinetic. E hoʻoheheʻe ʻia ka metala lithium ma ka ʻili o ka electrode maikaʻi ʻole ma muli o ka emi ʻana o ka helu hoʻokomo lithium graphite. Eia naʻe, ma hope o kahi manawa o ka mālama ʻana, hiki ke hoʻopili hou ʻia kēia ʻāpana o ka lithium metala i loko o ka graphite; i ka hoʻohana maoli ʻana, pōkole pinepine ka manawa o ka papa, a ʻaʻohe mea e hōʻoiaʻiʻo e hiki ke hoʻokomo hou ʻia ka lithium metala āpau i loko o ka graphite, no laila hiki ke hoʻomau ʻia kekahi lithium metala i loko o ka electrode maikaʻi ʻole. E hoʻopilikia ka ʻili o ka pākaukau lithium-ion i ka mana o ka pā lithium-ion a hiki ke hana i nā dendrites lithium e hoʻoweliweli i ka palekana o ka pā lithium-ion. No laila, e ho'āʻo e pale aku i ka hoʻopiʻi ʻana i ka pā lithium-ion ma nā haʻahaʻa haʻahaʻa. ʻO ka haʻahaʻa o kēia manawa, a ma hope o ka hoʻonohonoho ʻana, e hōʻoia i ka manawa kūpono e hoʻopau ai i ka lithium metala i ka electrode graphite maikaʻi ʻole.

E pili ana kēia ʻatikala i nā palapala ma lalo nei. Hoʻohana wale ʻia ka hōʻike e hoʻolauna a loiloi i nā hana ʻepekema pili, ke aʻo ʻana i ka lumi papa, a me ka noiʻi ʻepekema. ʻAʻole no ka hoʻohana pāʻoihana. Inā loaʻa iā ʻoe kekahi pilikia kope, e ʻoluʻolu e kelepona mai iā mākou.

1. Rate hiki o nā mea graphite e like me nā electrodes maikaʻi ʻole i ka lithium-ion capacitors, Electrochimica Acta 55 (2010) 3330 - 3335 , SRSivakkumar, JY Nerkar, AG Pandolfo

2. Lithium plating i loko o ka lithium-ion pākaukau i noiʻi ʻia e ka hoʻomaha hoʻomaha a me ka neutron diffraction in situ, Journal of Power Sources 342(2017) 17-23, Christian von Lüders, Veronika Zinth, Simon V.Erhard, Patrick J.Osswald, Michael Hofman , Ralph Gilles, Andreas Jossen

3. Lithium plating i loko o ka lithium-ion i nā mahana sub-ambient i noiʻi ʻia e in situ neutron diffraction, Journal of Power Sources 271 (2014) 152-159, Veronika Zinth, Christian von Lüders, Michael Hofmann, Johannes Hattendorff, Irmgard Buchberger, Simon Erhard, Joana Rebelo-Kornmeier, Andreas Jossen, Ralph Gilles