JP5522844B2 - 電気化学素子用電極およびリチウムイオン二次電池 - Google Patents
電気化学素子用電極およびリチウムイオン二次電池 Download PDFInfo
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- JP5522844B2 JP5522844B2 JP2010196468A JP2010196468A JP5522844B2 JP 5522844 B2 JP5522844 B2 JP 5522844B2 JP 2010196468 A JP2010196468 A JP 2010196468A JP 2010196468 A JP2010196468 A JP 2010196468A JP 5522844 B2 JP5522844 B2 JP 5522844B2
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- 239000002562 thickening agent Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
LixNi(1−y−z)CoyMzO2 (1)
[前記一般式(1)中、Mは、MnおよびAlのうちの少なくとも1種の元素であり、0.9≦x≦1.3、0<y<1、0<z<1およびy+z<1である]で表され、体積基準の粒度分布において、2つのピークトップを有しており、小粒径側のピーク(A)のピークトップが粒径2〜4μmの範囲内に存在し、かつ大粒径側のピーク(B)のピークトップが粒径8.8〜11μmの範囲内に存在しており、前記ピーク(A)における粒径の体積頻度をA、前記ピーク(B)における粒径の体積頻度をBとしたとき、0.18≦A/(A+B)≦0.45の関係を満たしており、累積体積50%の粒径が4.6〜10.3μmであるリチウム含有複合酸化物を活物質として使用し、水銀圧入法により求められる電極合剤層の細孔分布曲線において、2つのピークトップを有しており、小孔径側のピーク(a)のピークトップが細孔径140〜220nmの範囲内に存在し、かつ大孔径側のピーク(b)のピークトップが細孔径330〜910nmの範囲内に存在しており、前記ピーク(a)におけるピークトップの細孔容積をa(ml/g)、前記ピーク(b)におけるピークトップの細孔容積をb(ml/g)としたとき、0.26≦a/(a+b)≦0.53の関係を満たすことを特徴とするものである。
<リチウム含有複合酸化物の合成>
水酸化ナトリウムの添加によってpHを約12に調整したアンモニア水を反応容器に入れ、これを強攪拌しながら、この中に、硫酸ニッケル、硫酸コバルトおよび硫酸マンガンを、それぞれ、2.4mol/dm3、0.8mol/dm3、0.8mol/dm3の濃度で含有する混合水溶液と、25質量%濃度のアンモニア水とを、それぞれ、23cm3/分、6.6cm3/分の割合で、定量ポンプを用いて滴下して、NiとCoとMnとの共沈化合物(球状の共沈化合物)を合成した。なお、この際、反応液の温度は50℃に保持し、また、反応液のpHが12付近に維持されるように、6.4mol/dm3濃度の水酸化ナトリウム水溶液の滴下も同時に行い、更に窒素ガスを1dm3/分の流量でバブリングした。
前記リチウム含有複合酸化物96質量部と、バインダであるPVDFを10質量%の濃度で含むN−メチル−2−ピロリドン(NMP)溶液20質量部と、導電助剤である人造黒鉛1質量部およびケッチェンブラック1質量部とを、二軸混練機を用いて混練し、更にNMPを加えて粘度を調節して、正極合剤含有ペーストを調製した。
負極活物質である数平均粒子径が10μmの天然黒鉛97.5質量部と、バインダであるスチレンブタジエンゴム1.5質量部と、増粘剤であるカルボキシメチルセルロース1質量部とに、水を加えて混合し、負極合剤含有ペーストを調製した。この負極合剤含有ペーストを厚みが8μmの銅箔の両面に塗布し、乾燥させて負極合剤層を形成した後、カレンダー処理を行って、負極合剤層の厚みを調節し、銅箔の露出部にニッケル製のリード体を溶接して、所定の幅および長さになるように切断し、帯状の負極を作製した。なお、得られた負極の全厚は128μmであった。
ECとMECとDECとの容積比2:3:1の混合溶媒に、LiPF6を1mol/Lの濃度で溶解させて、非水電解液を調製した。
前記帯状の正極を、厚みが16μmの微孔性ポリエチレンセパレータ(空孔率:41%)を介して前記帯状の負極に重ね、渦巻状に巻回した後、扁平状になるように加圧して扁平状巻回構造の電極巻回体とし、この電極巻回体をポリプロピレン製の絶縁テープで固定した。次に、外寸が厚さ5.0mm、幅42mm、高さ61mmのアルミニウム合金製の角形の電池ケースに前記電極巻回体を挿入し、リード体の溶接を行うとともに、アルミニウム合金製の蓋板を電池ケースの開口端部に溶接した。続いて、蓋板に設けた注入口から非水電解液を注入し、その後注入口を封止して、図1に示す構造で、図2に示す外観のリチウムイオン二次電池を得た。また、非水電解液注入直後からの電池のインピーダンスの経時変化を測定し、インピーダンスが安定した時間を、非水電解液の含浸必要時間として評価した。
実施例1と同様に合成したリチウム含有複合酸化物から、粉砕する力および時間を変化させて、得られる2種類の粒子径およびその混合量を調整し、表1に示すD50、ピーク(A)およびピーク(B)のピークトップの粒径、並びにA/(A+B)の値を有するリチウム含有複合酸化物の混合粉体を得た。これらのリチウム含有複合酸化物の混合粉体を正極活物質に使用し、正極作製時のカレンダー処理の線圧を表1に示す通りにした以外は、実施例1と同様にして正極を作製し、これらの正極を用いた以外は、実施例1と同様にしてリチウムイオン二次電池を作製した。
2 負極
3 セパレータ
Claims (2)
- 集電体の片面または両面に活物質を含有する電極合剤層を有する電気化学素子用電極であって、
下記一般式(1)
LixNi(1−y−z)CoyMzO2 (1)
[前記一般式(1)中、Mは、MnおよびAlのうちの少なくとも1種の元素であり、0.9≦x≦1.3、0.1≦y≦0.25、0.05≦z≦0.35およびy+z≦0.5である]で表され、体積基準の粒度分布において、2つのピークトップを有しており、小粒径側のピーク(A)のピークトップが粒径2〜4μmの範囲内に存在し、かつ大粒径側のピーク(B)のピークトップが粒径8.8〜11μmの範囲内に存在しており、前記ピーク(A)における粒径の体積頻度をA、前記ピーク(B)における粒径の体積頻度をBとしたとき、0.18≦A/(A+B)≦0.45の関係を満たしており、累積体積50%の粒径が4.6〜10.3μmであるリチウム含有複合酸化物を活物質として使用し、
水銀圧入法により求められる電極合剤層の細孔分布曲線において、2つのピークトップを有しており、小孔径側のピーク(a)のピークトップが細孔径140〜220nmの範囲内に存在し、かつ大孔径側のピーク(b)のピークトップが細孔径330〜910nmの範囲内に存在しており、前記ピーク(a)におけるピークトップの細孔容積をa(ml/g)、前記ピーク(b)におけるピークトップの細孔容積をb(ml/g)としたとき、0.26≦a/(a+b)≦0.53の関係を満たすことを特徴とする電気化学素子用電極。 - 正極、負極、セパレータおよび非水電解液を有するリチウムイオン二次電池であって、
前記正極が、請求項1に記載の電気化学素子用電極であることを特徴とするリチウムイオン二次電池。
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KR101498886B1 (ko) * | 2006-12-26 | 2015-03-05 | 미쓰비시 가가꾸 가부시키가이샤 | 리튬 천이 금속계 화합물 분체, 그 제조 방법, 및 그 소성 전구체가 되는 분무 건조체, 그리고 그것을 사용한 리튬 이차 전지용 정극 및 리튬 이차 전지 |
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