TWI499119B - 鋰蓄電池用石墨系負極活性物質 - Google Patents
鋰蓄電池用石墨系負極活性物質 Download PDFInfo
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- TWI499119B TWI499119B TW100127983A TW100127983A TWI499119B TW I499119 B TWI499119 B TW I499119B TW 100127983 A TW100127983 A TW 100127983A TW 100127983 A TW100127983 A TW 100127983A TW I499119 B TWI499119 B TW I499119B
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- Prior art keywords
- negative electrode
- lithium secondary
- secondary battery
- active material
- electrode active
- Prior art date
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 92
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 80
- 229910052744 lithium Inorganic materials 0.000 title claims description 80
- 239000007773 negative electrode material Substances 0.000 title claims description 68
- 229910002804 graphite Inorganic materials 0.000 title claims description 65
- 239000010439 graphite Substances 0.000 title claims description 65
- 238000000034 method Methods 0.000 claims description 27
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
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- 229910052782 aluminium Inorganic materials 0.000 description 4
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- 150000004676 glycans Chemical class 0.000 description 2
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- WAHQBNXSPALNEA-UHFFFAOYSA-L lithium succinate Chemical compound [Li+].[Li+].[O-]C(=O)CCC([O-])=O WAHQBNXSPALNEA-UHFFFAOYSA-L 0.000 description 2
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- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
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- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
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Classifications
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
本發明係關於鋰蓄電池用石墨系負極活性物質、鋰蓄電池用負極、及鋰蓄電池。更詳細而言,本發明係關於即使為了獲得高電池電容而高密度地填充,充放電循環特性仍良好之鋰蓄電池用石墨系負極活性物質、含有該鋰蓄電池用石墨系負極活性物質之鋰蓄電池負極、以及具備該鋰蓄電池用負極之鋰蓄電池。又,本發明之鋰蓄電池意指鋰離子電容器。
行動設備等之電源主要係使用鋰蓄電池。行動設備等其功能多樣化使得消耗電力變大。因此,鋰蓄電池被要求增加其電池電容,同時提高充放電循環特性。該鋰蓄電池一般於正極活性物質中使用琥珀酸鋰等鋰鹽,於負極活性物質中使用石墨等。
為了增加電池電容,而考慮有例如提高負極中所用之碳質材料之電極填充密度之方法。然而,過去之使用碳質材料提高電極填充密度時,有引起碳質材料變形,使循環特性顯著降低之情況。
據此,已檢討藉由改良負極用碳質材料本身,而提高電池電容且改善循環特性。例如,專利文獻1或專利文獻2中記載特定結晶構造之複合石墨。專利文獻3記載併用特定結晶構造之石墨與特定結晶構造之氣相法碳纖維。又專利文獻4記載使作為聚合物原料之有機化合物附著於石墨等之碳質粒子上,使該有機化合物聚合,隨後在1800~3300℃下熱處理獲得之複合碳材料。
[專利文獻1]特開2007-141677號公報
[專利文獻2]WO2007/072858
[專利文獻3]特開2007-42620號公報
[專利文獻4]特開2005-158718號公報
關於上述專利文獻所揭示之碳材料,鋰蓄電池之電容及充放電循環特性已獲得改善。然而,由於對鋰蓄電池之要求性能逐年提高,故期望鋰蓄電池負極用之碳質材料之進一步改善。
因此,本發明之目的係提供一種電容高,且即使高密度填充,其充放電循環特性仍良好之鋰蓄電池用石墨系負極活性物質、含有該負極活性物質之鋰蓄電池用負極、以及具備該負極之鋰蓄電池。
本發明者等人為達成上述目的而積極檢討。其結果,發現混合調製以X射線繞射法測定之面間隔、結晶大小、及繞射峰之半值寬成為特定數值範圍之新穎鋰蓄電池用石墨系負極活性物質。因此,鋰蓄電池之負極中含有該負極活性物質時,發現可獲得電容高,且即使高密度填充其充放電特性仍良好之鋰蓄電池。本發明係基於該見解進行檢討因而完成者。
亦即,本發明為包含以下者。
[1] 一種鋰蓄電池用石墨系負極活性物質,其特徵為於粉末X射線繞射中,d002
為0.3354nm以上且0.337nm以下,Lc(004)未達100nm,La(110)為100nm以上,且出現在繞射角(2θ):44°~45°之源自(101)面之峰之半值寬為0.65°以上。
[2] 如前述[1]所記載之鋰蓄電池用石墨系負極活性物質,其中粉末X射線繞射中之峰強度比I(100)/I(101)為0.7以上且1以下。
[3] 如前述[1]或[2]所記載之鋰蓄電池用石墨系負極活性物質,其中將包含該負極活性物質與黏合劑而成之合劑塗佈於銅箔上,經乾燥,接著藉由加壓成形而形成密度1.5g/cm3
以上且1.6g/cm3
以下之合劑層,以X射線繞射法測定該合劑層時之峰強度比I(110)/I(004)為0.2以上。
[4] 如前述[1]~[3]中任一項所記載之鋰蓄電池用石墨系負極活性物質,其中BET比表面積為5m2
/g以下,且體積平均粒徑D50
為3μm以上且30μm以下。
[5] 如前述[1]~[4]中任一項所記載之鋰蓄電池用石墨系負極活性物質,其中於粉末X射線繞射中出現在繞射角(2θ):44°~45°之源自(101)面之峰之半值寬為0.65°以上且2°以下。
[6] 如前述[1]~[5]中任一項所記載之鋰蓄電池用石墨系負極活性物質,其係經表面處理而成。
[7] 如前述[1]~[5]中任一項所記載之鋰蓄電池用石墨系負極活性物質,其係以軟化點200~350℃且固定碳50~80質量%之瀝青進行表面處理而成。
[8] 如前述[7]所記載之鋰蓄電池用石墨系負極活性物質,其中前述瀝青之體積平均粒徑D50
為1μm~10μm。
[9] 如前述[7]所記載之鋰蓄電池用石墨系負極活性物質,其中前述瀝青為光學等向性者。
[10] 一種如前述[1]~[9]中任一項所記載之鋰蓄電池用石墨系負極活性物質之製造方法,其包含將含有API比重1~5度、生瀝青(asphallenes)含量10~50%、樹脂含量5~30%及硫含量1~12%之原油減壓蒸餾殘渣予以焦炭化而獲得焦炭,將該焦炭粉碎獲得碳粉體,在1000~3500℃下加熱處理該碳粉體。
[11] 如前述[10]所記載之製造方法,其進而包含以機械熔合(mechano-fusion)或濕式法進行表面處理。
[12] 如前述[10]或[11]所記載之製造方法,其中焦炭之含水率為1.0%以下。
[13] 一種鋰蓄電池用負極,其係含有如前述[1]~[9]中任一項所記載之鋰蓄電池用石墨系負極活性物質而成。
[14] 如前述[13]所記載之鋰蓄電池用負極,其係進而含有纖維徑5nm以上0.2μm以下之氣相法碳纖維而成。
[15] 一種鋰蓄電池,其係具備如前述[13]或[14]所記載之鋰蓄電池用負極。
[16] 如前述[15]所記載之鋰蓄電池,其係具備由碳酸伸乙酯、碳酸二乙酯、碳酸二甲酯、碳酸甲基乙酯、碳酸伸丙酯、碳酸丁烯酯、γ-丁內酯及碳酸伸乙烯酯所組成群組選出之至少一種溶劑。
[17] 一種交通機關,其係具備如前述[15]或[16]所記載之鋰蓄電池。
[18] 一種發電系統,其係具備如前述[15]或[16]所記載之鋰蓄電池。
[19] 一種電氣‧電子機器,其係具備如前述[15]或[16]所記載之鋰蓄電池。
鋰蓄電池之負極中含有本發明之鋰蓄電池用石墨系負極活性物質時,可獲得電容高,且即使高密度填充,其充放電循環特性仍良好之鋰蓄電池。
本發明之鋰蓄電池用石墨系負極活性物質於粉末X射線繞射中,d002
為0.3354nm以上0.337nm以下,較好為0.3359nm以上0.3368nm以下。d002
係顯示石墨之結晶性之高低。
又,d002
係基於石墨粉末之002繞射線,由Bragg之式d=λ/sinθc計算出之面間隔。
本發明之負極活性物質於粉末X射線繞射中,Lc(004)未達100nm,較好為40nm以上85nm以下。又,本發明之負極活性物質於粉末X射線繞射中,La(110)為100nm以上。
又,Lc(004)係基於石墨粉末之004繞射線,算出之結晶c軸方向之厚度。La(110)係基於石墨粉末之110繞射線,所算出之結晶a軸方向之寬度。
本發明之負極活性物質於粉末X射線繞射中,出現在繞射角(2θ):44°~45°之源自(101)面之峰之半值寬B101
為0.65°以上,較好為0.65°以上2°以下,更好為0.7°以上1.5°以下。
源自(101)面之峰之半值寬B101
為0.65°以上,係顯示作為峰係較寬廣。所謂該峰寬廣被視為顯示石墨結晶之ABA堆積構造之亂度。已知鋰離子插入於石墨層間時,由ABA堆積構造變化成AAA堆積構造。ABA堆積構造混亂時,推測插入鋰離子時石墨堆積構造之變化可能無法在較低之能量下進行。
又,本發明之負極活性物質在粉末X射線繞射中之峰強度比I(100)/I(101)較好為1以下,更好為0.7以上1以下,又更好為0.75以上0.95以下。
而且,本發明之負極活性物質係將包含該負極活性物質與黏合劑而成之合劑塗佈於銅箔上,經乾燥,接著藉由加壓成形而形成密度1.5g/cm3
以上且1.6g/cm3
以下之合劑層,且以X射線繞射法測定該合劑層時之峰強度比I(110)/I(004)較好為0.2以上,更好為0.35以上0.9以下。以該測定法獲得之峰強度比I(110)/I(004)係顯示石墨粉末之配向性。該值愈大則顯示配向性愈低。
又,本發明之負極活性物質之BET比表面積較好為5m2
/g以下,更好為1~4.5m2
/g。BET比表面積為5m2
/g以下時,與電解液之不期望副反應難以進展,且充放電循環特性之劣化亦難以進展。
再者,本發明之負極活性物質之體積平均粒徑D50
較好為3μm以上且30μm以下,更好為4μm以上且25μm以下,又更好為4μm以上且20μm以下。具有該範圍之體積平均粒徑D50
時電極表面之平滑性變良好且與電解液之不期望副反應難以進展。
本發明之負極活性物質可例如以下列之方法獲得。
首先,減壓蒸餾委內瑞拉產原油獲得殘渣。該殘渣之API比重較好為1~5度,生瀝青(asphallenes)含量較好為10~50%,樹脂含量較好為5~30%,且硫含量較好為1~12%。
使該殘渣焦化獲得焦炭。焦化方法可為延遲焦化法,亦可為流體焦化法。以水切出所得焦炭,將其加熱,並乾燥至含水率較好成為1.0%以下。
粉碎經乾燥之焦炭塊,並經分級,獲得焦炭粉末。粉碎方法並無特別限制,列舉為例如錘磨法、針磨法、噴射研磨法、棒研磨法、ACM磨碎機等裝置之方法。分級後之碳粉體之體積平均粒徑D50
較好為3μm以上30μm以下,更好為4μm以上25μm以下,又更好為4μm以上20μm以下。
該碳粉體較好在1000~3500℃,更好在2000~3400℃,又更好在2500~3300℃經加熱處理而石墨化。如此可獲得本發明之負極活性物質。
本發明之負極活性物質亦可為其表面施以處理者。該表面處理列舉為藉由機械融合(mechanofusion)法等進行表面融合、以濕式法等進行表面被覆等。
至於濕式法有例如特開2005-158718號公報中記載之方法。具體而言,為包含使作為聚合物原料之有機化合物附著及/或含浸於負極活性物質之表面上,接著使有機化合物聚合,隨後在1800~3300℃下經熱處理之方法,或者包含使樹脂材料之溶液附著及/或含浸於負極活性物質之表面,並經乾燥,接著在1800~3300℃熱處理之方法。
又,機械融合法之例為包含將負極活性物質與不同種之碳材料或樹脂材料倒入可高速旋轉混合之裝置中,對負極活性物質與不同種碳材料或樹脂材料施加機械能,引發機械化學反應,接著視需要在900~2000℃熱處理之方法。本發明較好為利用機械融合法進行表面處理。
負極活性物質之表面處理中係使用石油系瀝青、石碳系瀝青、煤渣等之碳材料,或酚樹脂、矽烷樹脂等之樹脂材。石油系瀝青或石碳系瀝青有光學等向性者與光學異向性者。本申請案之說明書之實施例中係使用光學等向性者。表面處理中使用之瀝青之軟化點較好為200~350℃,固定碳較好為50~80質量%,體積平均粒徑D50
較好為1μm~10μm。該表面處理中使用之瀝青量相對於負極活性物質100質量份,較好為0.1~50質量份,更好為0.1~10質量份。
又,本發明之鋰蓄電池用石墨系負極活性物質只要是具有如上述之特性值者即可,可為由單一種碳材料所構成者,亦可為由不同種之複數種碳材料所構成者。
本發明之鋰蓄電池用負極為含有本發明之負極活性物質者。
鋰蓄電池用負極中,該負極活性物質通常含於負極活性物質層中。該負極活性物質層為以各種成形法使含有前述負極活性物質、黏合劑及視需要調配之添加劑之合劑成形而成者。又,該負極活性物質層中,通常層合有用以使端子或導電線等之通電變容易之集電體。
黏合劑列舉為聚乙烯、聚丙烯、乙烯丙烯三聚物、丁二烯橡膠、苯乙烯丁二烯橡膠、丁基橡膠、聚四氟乙烯、聚(甲基)丙烯酸酯、聚偏氟化乙烯、聚環氧乙烷、聚環氧丙烷、聚表氯醇、聚磷腈(polyphosphazene)、聚丙烯腈等。
視需要調配於負極活性物質層中之添加劑列舉為導電性賦予材料、離子透過性化合物、增黏劑、分散劑、滑劑、活性碳等。
導電性賦予材料列舉為銀粉等之導電性金屬粉;高爐碳黑、爐炭黑、乙炔黑等導電性碳粉;碳奈米管、碳奈米纖維、氣相法碳纖維等。本發明之負極中,較好含有氣相法碳纖維作為添加劑。氣相法碳纖維之纖維徑較好為5nm以上0.2μm以下。氣相法碳纖維之含量相對於負極活性物質層之質量較好為0.1~10質量%。至於離子透過性化合物列舉為甲殼素、殼聚醣等多糖類,或該多糖類之交聯物等。增黏劑列舉為羧基甲基纖維素、聚乙烯醇等。
負極活性物質層係藉由例如將糊狀之合劑塗佈於集電體上,並經乾燥、加壓成形,或將粉粒狀之合劑加壓成形於集電體上而獲得。負極活性物質層之厚度通常為0.04mm以上0.15mm以下。藉由調整成形時施加之壓力可獲得任意電極密度之負極活性物質層。成形時施加之壓力較好為1t/cm2
~3t/cm2
左右。
至於集電體列舉為導電性金屬箔、導電性金屬之網、導電性金屬之沖孔金屬等。導電性金屬係使用包含銅、鋁、鎳等者。負極用集電體較好為含銅者。
本發明之鋰蓄電池為具備本發明之鋰蓄電池用負極者。又,本發明之鋰蓄電池意指鋰離子電容器。
本發明之鋰蓄電池進而具備正極。正極可使用鋰蓄電池中過去以來所使用者。正極通常由含有正極活性物質之正極活性物質層、與層合於正極活性物質層上之集電體所構成。至於正極活性物質列舉為LiNiO2
、LiCoO2
、LiMn2
O4
等。該正極活性物質層亦可進一步含有過去習知之正極活性物質用之添加劑。正極用集電體以含鋁者較佳。
鋰蓄電池通常係將正極與負極浸漬於電解質中。電解質可為液體、凝膠或固體之任一種。
液體電解質列舉為鋰鹽之非水性溶劑溶液。鋰鹽列舉為LiClO4
、LiPF6
、LiAsF6
、LiBF4
、LiSO3
SF3
、CH3
SO3
Li、CF3
SO3
Li等。液體電解質中使用之非水性溶劑較好為由碳酸乙二酯、碳酸二乙酯、碳酸二甲酯、碳酸甲酯乙酯、碳酸丙二酯、碳酸丁二酯、γ-丁內酯、及碳酸伸乙烯酯所組成群組選出之至少一種。
固體電解質或凝膠電解質列舉為使用磺化苯乙烯-烯烴共聚物等之高分子電解質、使用聚環氧乙烷與MgClO4
之高分子電解質、具有三亞甲基氧化物構造之高分子電解質等。高分子電解質中所用之非水性溶劑較好為由碳酸伸乙酯、碳酸二乙酯、碳酸二甲酯、碳酸甲基乙酯、碳酸伸丙酯、碳酸伸丁酯、γ-丁內酯、及碳酸伸乙烯酯所組成群組選出之至少一種。
於正極與負極之間視需要設置隔離材。隔離材列舉為例如不織布、織布、微細孔質薄膜等,或組合該等而成者等。
本發明之鋰蓄電池可使用於各種領域。例如,個人電腦、桌上型電腦、筆記型電腦、行動電話、無線電話機、電子記事本、電子辭典、PDA(個人數位助理)、電子測量計、電子鎖、電子條碼、電力儲存裝置、電動工具、玩具、數位相機、數位錄影機、AV設備、吸塵器等電氣‧電子設備;電動車、油電混合車、電動機車、油電混合機車、電動自行車、電動輔助自行車、鐵路設備、飛機、船舶等交通設備;太陽光發電系統、風力發電系統、潮力發電系統、地熱發電系統等發電系統等。
以下列舉實施例更具體說明本發明,但本發明並不限於該等實施例。
鋰蓄電池用石墨系負極活性物質之物性係以如下方法測定。
以粉末X射線繞射法求得。d002
係基於002繞射線,由Bragg之式d=λ/sinθc算出之面間隔。Lc(004)為基於004繞射線,算出之結晶c軸方向之厚度。La(110)係基於110繞射線,算出之結晶a軸方向之寬度。I(100)/I(101)為100繞射線之峰強度相對於101繞射線之峰強度之比。B101
為出現於繞射角(2θ):44°~45°之101繞射線之峰半值寬。
以使KUREHA公司製造之聚偏氟化乙烯(L#9130;正-甲基-2-吡咯烷酮溶液)成為固體成分5質量%之方式,邊少量添加負極活性物質邊混練。接著,添加正-甲基-2-吡咯烷酮加以混練,調整至具有足夠流動性。使用日本精機製作所公司製造之脫泡捏合機NBK-1,在500rpm進行混練5分鐘,獲得糊料狀之合劑。使用自動塗佈機與間隙250μm之刮板,將前述合劑塗佈於銅箔上。
將塗佈有合劑之銅箔置於約80℃之加熱板上去除水分。隨後,以真空乾燥機在120℃乾燥6小時。乾燥後,以壓製機加壓成形以使由合劑中之固體成分之質量與塗膜乾燥體積算出之電極密度成為1.5g/cm3
以上1.6g/cm3
以下,層合合劑層與銅箔獲得電極片。將電極片切成適當大小,貼附於X射線繞射測定用之玻璃胞上,以X射線繞射法測定。接著,算出峰強度比I(110)/I(004)。峰強度比I(110)/I(004)表示石墨之配向性。
藉由利用氮氣吸附之BET法進行解析,算出比表面積。
將石墨以極小型藥匙兩匙份與非離子性界面活性劑(TRITON-X)2滴添加於水50ml中,以超音波分散3分鐘。將該分散液倒入Malvern公司製造之雷射繞射式粒度分布測定器(Mastersizer)中,測定粒度分布,求得體積平均粒徑D50
。
減壓蒸餾委內瑞拉產原油獲得殘渣。該殘渣之API比重為2.3度,生瀝青含量為25%,樹脂含量為15%,且硫含量為6.0%。將該殘渣倒入延遲焦化器中,經焦化,獲得焦炭。以水切出所得焦炭,使之在120℃加熱,乾燥至水分含有率成為1.0%以下。
以Hosokawa Micron公司製造之錘磨機粉碎經乾燥之焦炭塊,以日清工程公司製造之渦流分級機-TC-15N進行氣流分級,獲得體積平均粒徑D50
為17μm之碳粉體。
將該碳粉體填充於石墨製坩堝中,以Acheson爐在3200℃加熱處理,獲得石墨A1。物性示於表1。圖1顯示石墨A1之粉末X射線繞射。
除使用以氣流分級獲得體積平均粒徑D50
為5μm之碳粉末,以該等代替體積平均粒徑D50
為17μm之碳粉末以外,餘以與實施例1相同之方法,獲得石墨B1。物性示於表1。
混合軟化點約275℃、固定碳65質量%及體積平均粒徑D50
為5μm之石油系光學等向性瀝青5質量份,及石墨A1 95質量份。將該混合物倒入Hosokawa Micron公司製造之機械融合系統中,經高速旋轉。接著,使之在氮氣氛圍下於1200℃熱處理1小時。冷卻後,通過網目45μm之篩網獲得石墨A2。又,機械融合為對複數種不同之材料粒子施加某種機械能,引起機械化學反應,創造新材料之技術。物性示於表1。
除使用石墨B1代替石墨A1以外,餘以與實例3相同方法,獲得石墨B2。物性示於表1。
準備球狀天然石墨(以下記為石墨C1)、介晶相碳(以下記為石墨D)及鱗片狀人造石墨(以下記為石墨E)做為比較例。該等均為市售品。
另外,除使用石墨C1代替石墨A1以外,餘以與實施例3相同之方法,獲得石墨C2。該等之物性示於表1。
以實施例1~4及比較例1~4中準備之石墨作為各負極活性物質。
使用該等負極活性物質,以下述方法製造鋰蓄電池,且測定200次充放電循環後之放電電容保持率(%)。結果示於表2。
在保持於露點-80℃以下之乾燥氬氣氛圍下之手套箱內進行下述操作。
將N-甲基-2-吡咯烷酮添加於琥珀酸鋰(日本化學工業製造之正極材C-10)95質量份、黏合劑(聚偏氟化乙烯:PVDF)3質量份、及導電材(乙炔黑)5質量份中,獲得漿料狀合劑。將該合劑塗佈於厚度25μm之鋁箔上。以真空乾燥機在120℃乾燥塗佈有合劑之鋁箔6小時。乾燥後,以壓製機加壓成形使得自合劑中之固體成分質量與塗膜乾燥體積算出之電極密度約為3.5g/cm3
,獲得正極。至於負極係使用配向性評價中製作之電極片。
於成為圓筒形之SUS304製造之支撐外裝材中,以分隔材、板螺釘、負極、隔離材(聚丙烯製造之微孔隙膜「CELGARD 2400」,CELGARD公司製造)及正極依此順序層合重疊。於其上載置成為圓筒形之SUS304製之上蓋外裝材。接著,使用造幣機,封裝支撐外裝材與上蓋外裝材,獲得評價用硬幣電池。針對一種負極活性物質製造5個硬幣電池,供評價試驗。
使用上述硬幣電池進行如下之定電流定電壓放電試驗。
初次與第二次之充放電循環如下進行。
以0.17mA/cm2
自靜止電位定電流充電至4.2V為止,且自到達4.2V之時點以4.2V進行定電壓充電,於電流值低至25.4μA之時點停止充電。接著,以0.17mA/cm2
進行定電流放電,在電壓2.7V下截止。
第三次以後之充放電循環如下進行。
以0.34mA/cm2
(相當於0.2C)自靜止電位定電流充電至4.2V為止,自到達4.2V之時點以4.2V進行定電壓充電,於電流值低至20μA之時點停止充電。接著,以1.7mA/cm2
(相當於1.0C)進行定電流放電,在電壓2.7V下截止。
接著,測定第200次放電電容相對於第三次放電電容之比例。針對5個硬幣電池進行該測定,求得其平均值作為「200次之充放電循環後之放電電容保持率(%)」。
如表2所示,利用本發明之鋰蓄電池用石墨系負極活性物質,可知獲得具有良好充放電循環特性之鋰蓄電池。
圖1為顯示實施例1中獲得之本發明之鋰蓄電池用石墨系負極活性物質之粉體X射線繞射之圖。
Claims (17)
- 一種鋰蓄電池用石墨系負極活性物質,其特徵為於粉末X射線繞射中,d002 為0.3354nm以上且0.337nm以下,Lc(004)未達100nm,La(110)為100nm以上,且出現在繞射角(2θ):44°~45°之源自(101)面之峰之半值寬為0.65°以上。
- 如申請專利範圍第1項之鋰蓄電池用石墨系負極活性物質,其中粉末X射線繞射中之峰強度比I(100)/I(101)為0.7以上且1以下。
- 如申請專利範圍第1項之鋰蓄電池用石墨系負極活性物質,其中將包含該負極活性物質與黏合劑而成之合劑塗佈於銅箔上,經乾燥,接著藉由加壓成形而形成密度1.5g/cm3 以上且1.6g/cm3 以下之合劑層,以X射線繞射法測定該合劑層時之峰強度比I(110)/I(004)為0.2以上。
- 如申請專利範圍第1項之鋰蓄電池用石墨系負極活性物質,其中BET比表面積為5m2 /g以下,且體積平均粒徑D50 為3μm以上且30μm以下。
- 如申請專利範圍第1項之鋰蓄電池用石墨系負極活性物質,其中於粉末X射線繞射中出現在繞射角(2θ):44°~45°之源自(101)面之峰之半值寬為0.65°以上且2°以下。
- 如申請專利範圍第1至5項中任一項之鋰蓄電池用石墨系負極活性物質,其係經表面處理而成。
- 如申請專利範圍第1至5項中任一項之鋰蓄電池用石墨系負極活性物質,其係以軟化點200~350℃且固定碳50~80質量%之瀝青進行表面處理而成。
- 如申請專利範圍第7項之鋰蓄電池用石墨系負極活性物質,其中前述瀝青之體積平均粒徑D50 為1μm~10μm。
- 如申請專利範圍第7項之鋰蓄電池用石墨系負極活性物質,其中前述瀝青為光學等向性者。
- 一種如申請專利範圍第1至9項中任一項之鋰蓄電池用石墨系負極活性物質之製造方法,其包含將含有API比重1~5度、生瀝青含量10~50%、樹脂含量5~30%及硫含量1~12%之原油減壓蒸餾殘渣予以焦炭化而獲得焦炭,將該焦炭粉碎獲得碳粉體,在1000~3500℃下加熱處理該碳粉體。
- 如申請專利範圍第10項之製造方法,其進而包含以機械熔合(mechano-fusion)或濕式法進行表面處理。
- 如申請專利範圍第10項之製造方法,其中焦炭之含水率為1.0%以下。
- 一種鋰蓄電池用負極,其係含有如申請專利範圍第1至9項中任一項之鋰蓄電池用石墨系負極活性物質而成。
- 如申請專利範圍第13項之鋰蓄電池用負極,其係進而含有纖維徑5nm以上0.2μm以下之氣相法碳纖維而成。
- 一種鋰蓄電池,其係具備如申請專利範圍第13或14項之鋰蓄電池用負極。
- 如申請專利範圍第15項之鋰蓄電池,其係具備由碳酸伸乙酯、碳酸二乙酯、碳酸二甲酯、碳酸甲基乙酯、碳酸伸丙酯、碳酸丁烯酯、γ-丁內酯及碳酸伸乙烯酯所組成群組選出之至少一種溶劑。
- 一種交通機關、發電系統或電氣‧電子機器,其係具備如申請專利範圍第15或16項之鋰蓄電池。
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- 2011-08-05 CN CN2011800383018A patent/CN103053054A/zh active Pending
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JPWO2012017676A1 (ja) | 2013-10-03 |
KR20130041226A (ko) | 2013-04-24 |
EP2602850A4 (en) | 2016-12-21 |
US8790824B2 (en) | 2014-07-29 |
CN103053054A (zh) | 2013-04-17 |
US20130130127A1 (en) | 2013-05-23 |
EP2602850A1 (en) | 2013-06-12 |
EP2602850B1 (en) | 2019-03-06 |
WO2012017676A1 (ja) | 2012-02-09 |
KR101504614B1 (ko) | 2015-03-20 |
TW201225396A (en) | 2012-06-16 |
JP5960052B2 (ja) | 2016-08-02 |
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