JP2012521074A - 少なくとも3種のカソード材料の混合物を有する非水電気化学セル - Google Patents
少なくとも3種のカソード材料の混合物を有する非水電気化学セル Download PDFInfo
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- JP2012521074A JP2012521074A JP2012500918A JP2012500918A JP2012521074A JP 2012521074 A JP2012521074 A JP 2012521074A JP 2012500918 A JP2012500918 A JP 2012500918A JP 2012500918 A JP2012500918 A JP 2012500918A JP 2012521074 A JP2012521074 A JP 2012521074A
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- electrochemical cell
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- aqueous
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Images
Classifications
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- H01M10/052—Li-accumulators
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
Description
本開示に基づき、また本明細書の以下において更に詳述するように、フッ素化炭素と、少なくとも2種の追加的な金属酸化物のカソード材料との混合物を含むカソード材料とを用いると、非水電気化学セルの1つ以上の性能特性が改善され、または強化され得ることを発見した(ここで、少なくとも2種の追加的な金属酸化物のカソード材料(または得られるその混合物)のうちの一方または両方の作動電圧は、フッ素化炭素材料の作動電圧よりも少なくとも約500mV低く、いくつかの実施形態の作動電圧は、フッ素化炭素材料の作動電圧よりも約550、約600、約650、約700または実に約750mV低いことがある(当技術分野で周知の方法で測定した))。更に詳細には、カソード材料が、フッ素化炭素(即ち、本明細書で更に詳述する(CFx)n)と、銅の酸化物(例えばCuOまたはCu2O)と、マンガンの酸化物(例えばMnO2であり、天然MnO2(NMD)、化学MnO2(CMD)および/または電解MnO2(EMD)の形態のもの)の混合物を含む(或いはそれらから成る、またはそれらから基本的に構成される)とき、かかる非水セルの性能が改善され、または強化され得ることを発見した。
以上を操作または最適化することで、電気化学セルの寿命終末期の挙動を改善または強化できる。更に詳細には、これら因子の1つ以上を操作または最適化することで、電気化学セルはある期間の使用または放電後において電圧の平坦域を保有するまたは示すようになり、それが有用な寿命終末期の指標として機能し得る。この点において、フッ素化炭素の放電電圧は通常約2.5ボルト(V)〜約2.8Vであり、放電率に依存することに更に留意すべきである。その一方、例えば、本開示のカソード材料中に存在する銅の酸化物(例えばCuOまたはCu2O)は、約1.6V〜約2.3Vの間で電圧平坦域を示すことがあり、および/または本開示のカソード材料中に存在するマンガンの酸化物(例えばMnO2)は、約1.7V〜約2.4Vの間で電圧平坦域を示すことがある。
カソード材料の様々な成分(例えばフッ素化炭素、銅の酸化物、マンガンの酸化物等)は、商業的供給源から入手することができ(例えば、CFxはロデスター社(ニュージャージー州)から市販されているグレードPC/10とすることができ、MnO2はデルタEMD株式会社(南アフリカ)から市販されているTL−グレードの電解二酸化マンガンとすることができ、ナノ−CuOはアルファ・エイサー社(米国)の酸化銅とすることができる)、当業者に周知の方法を用いて調製することができることに留意すべきである。
カソード材料の成分(例えば、フッ素化炭素および銅の酸化物やマンガンの酸化物等の少なくとも2種の追加的なカソード材料)の正確な組成、および/またはカソード材料そのもの(例えば、フッ素化炭素と、たとえば銅の酸化物およびマンガンの酸化物等の少なくとも2種の追加的なカソード材料)、および/またはそれらの形態(例えば粒径)を、所望の性能特性および/またはそれを有する電気化学セルの所望の最終用途のアプリケーションに応じて最適化するように選択してもよいことに留意すべきである。
Claims (22)
- アノードと、
フッ素化炭素、銅の酸化物および酸化マンガンの酸化物の混合物を含むカソード材料を含むカソードと、
該アノードと該カソードとの間に配置されたセパレータと、
該アノード、該カソードおよび該セパレータと流体連結した非水電解質と
を具える非水電気化学セル。 - 前記銅の酸化物が、CuO、Cu2Oまたはそれらの混合物である請求項1に記載の非水電気化学セル。
- 前記マンガンの酸化物が、MnO2である請求項1に記載の非水電気化学セル。
- 前記マンガンの酸化物対前記銅の酸化物の重量比が、約1:1〜約3:1の間である請求項1に記載の非水電気化学セル。
- 前記銅の酸化物対前記マンガンの酸化物の重量比が、約1:1〜約4.5:1の間である請求項1に記載の非水電気化学セル。
- 前記銅の酸化物の粒径が、約15〜約45ナノメートルの間である請求項1に記載の非水電気化学セル。
- 前記カソード材料の混合物中のフッ素化炭素の濃度は、該カソード混合物の全重量に対して少なくとも約50重量%である請求項1に記載の非水電気化学セル。
- 前記カソード材料の混合物中のフッ素化炭素の濃度は、該カソード混合物の全重量に対して約60重量%〜約95重量%である請求項1に記載の非水電気化学セル。
- 前記フッ素化炭素は、式:CFx[式中、xは約0.1〜約1.9である]を有する請求項1に記載の非水電気化学セル。
- 前記フッ素化炭素は、式:(CFx1)nおよび(CFx2)m[式中、x1は約0.8〜約1.2の間であり、x2は約0.4〜約0.8の間であり、nは約1〜約5の間であり、mは約1〜約5の間である]を有する材料の混合物である請求項9に記載の非水電気化学セル。
- 前記非水電解質が、炭酸ジメチル(DMC)、炭酸ジエチル、1,2−ジメトキシエタン(DME)、テトラヒドロフラン(THF)、酢酸メチル(MA)、ジグリム、トリグリム、テトラグリム、プロピレンカーボネート(PC)、エチレンカーボネート(EC)、アセトニトリル、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、γ−ブチロラクトン(GBL)およびN−メチル−ピロリドン(NMP)から成る群より選択される有機溶媒、またはその2種以上の混合物を含む請求項1に記載の非水電気化学セル。
- 前記非水電解質は、式:MM’F6またはMM’F4[式中、Mはアノード中の少なくとも一種の金属と同一のアルカリ金属であり、M’はリン、ヒ素、アンチモンおよびホウ素から成る群より選択される元素である]を有する塩を含む請求項11に記載の非水電気化学セル。
- 前記塩が、LiPF6、LiAsF6、LiSbF6、LiBF4、LiClO4、LiAlCl4、LiGaCl4、LiC(SO2CF3)3、LiB(C6H4O2)2、LiN(CF3SO2)2およびLi(CF3SO3)並びにそれらの混合物から成る群より選択される請求項12に記載の非水電気化学セル。
- 前記非水電解質は塩を含み、有機溶媒中の該塩の濃度が約0.5M〜約2.5Mの範囲内である請求項13に記載の非水電気化学セル。
- 前記アノードが、元素の周期表のIA族またはIIA族から選択される金属を含む請求項1に記載の非水電気化学セル。
- 前記アノードが、リチウム、マグネシウム、ナトリウムおよびカリウムから成る群より選択される金属を含む請求項16に記載の非水電気化学セル。
- 前記アノードが、Li−Mg、Li−Al、Li−Al−Mg、Li−Si、Li−BおよびLi−Si−Bから成る群より選択される合金または金属間化合物を含む請求項16に記載の非水電気化学セル。
- 前記セルは、約2.0ボルトで少なくとも約2.7Ah/cm3の容積比容量を示す請求項1に記載の非水電気化学セル。
- 前記セルは、約1.5ボルトで少なくとも約2.9Ah/cm3の容積比容量を示す請求項1に記載の非水電気化学セル。
- 前記カソード材料は、カソード材料の全重量に対してフッ素化炭素を約81重量%、基本的に銅の酸化物とマンガンの酸化物から構成される混合物を約12重量%、結合剤材料を約3重量%、および導電性添加剤を約4重量%含む、請求項1に記載の非水電気化学セル。
- 前記フッ素化炭素、銅の酸化物およびマンガンの酸化物のカソード材料の混合物が示す容積比容量は、フッ素化炭素のカソード材料だけの容積比容量と比べて少なくとも約10%高い請求項1に記載の非水電気化学セル。
- 前記フッ素化炭素、銅の酸化物およびマンガンの酸化物のカソード材料の混合物が示す寿命終末期の指示は、フッ素化炭素のカソード材料だけの寿命終末期の指示と比べて少なくとも約5%長い請求項1に記載の非水電気化学セル。
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JPWO2014181778A1 (ja) * | 2013-05-09 | 2017-02-23 | 旭硝子株式会社 | 正極材料、及びその製造方法 |
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US8623553B2 (en) | 2014-01-07 |
US20100310908A1 (en) | 2010-12-09 |
EP2409348B1 (en) | 2015-07-01 |
WO2010107877A1 (en) | 2010-09-23 |
JP5528534B2 (ja) | 2014-06-25 |
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