JP2017147222A - リチウムイオン電池 - Google Patents
リチウムイオン電池 Download PDFInfo
- Publication number
- JP2017147222A JP2017147222A JP2017021119A JP2017021119A JP2017147222A JP 2017147222 A JP2017147222 A JP 2017147222A JP 2017021119 A JP2017021119 A JP 2017021119A JP 2017021119 A JP2017021119 A JP 2017021119A JP 2017147222 A JP2017147222 A JP 2017147222A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- electrode active
- lithium ion
- positive electrode
- negative electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 213
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- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- ZKIAYSOOCAKOJR-UHFFFAOYSA-M lithium;2-phenylethenesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 ZKIAYSOOCAKOJR-UHFFFAOYSA-M 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- NUMHUJZXKZKUBN-UHFFFAOYSA-N methyl 4-ethenylbenzoate Chemical compound COC(=O)C1=CC=C(C=C)C=C1 NUMHUJZXKZKUBN-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 125000006203 morpholinoethyl group Chemical group [H]C([H])(*)C([H])([H])N1C([H])([H])C([H])([H])OC([H])([H])C1([H])[H] 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
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- 238000007747 plating Methods 0.000 description 1
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- 229920001088 polycarbazole Polymers 0.000 description 1
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- 229920000915 polyvinyl chloride Polymers 0.000 description 1
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- MEZLKOACVSPNER-GFCCVEGCSA-N selegiline Chemical compound C#CCN(C)[C@H](C)CC1=CC=CC=C1 MEZLKOACVSPNER-GFCCVEGCSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- MXNUCYGENRZCBO-UHFFFAOYSA-M sodium;ethene;2-methylprop-2-enoate Chemical compound [Na+].C=C.CC(=C)C([O-])=O MXNUCYGENRZCBO-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
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- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- 239000005028 tinplate Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 229920001567 vinyl ester resin Polymers 0.000 description 1
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Images
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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
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Sealing Battery Cases Or Jackets (AREA)
- Cell Electrode Carriers And Collectors (AREA)
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Abstract
Description
CH2=C(R1)COOR2 (1)
[式(1)中、R1は水素原子又はメチル基であり、R2は炭素数4〜36の分岐アルキル基である。]
数平均分子量は、以下の条件でゲルパーミエーションクロマトグラフィー(以下GPCと略記)測定により求めることができる。
・装置:Alliance GPC V2000(Waters社製)
・溶媒:オルトジクロロベンゼン
・標準物質:ポリスチレン
・検出器:RI
・サンプル濃度:3mg/ml
・カラム固定相:PLgel 10μm、MIXED−B 2本直列(ポリマーラボラトリーズ社製)
・カラム温度:135℃
(実施例)
撹拌機、温度計、還流冷却管、滴下ロート及び窒素ガス導入管を付した4つ口フラスコにN,N−ジメチルホルムアミド(以下、DMFと略記)70部を仕込み75℃に昇温した。次いで、メタクリル酸2−エチルヘキシル40部、メタクリル酸45部、メタクリル酸メチル15部、スチレンスルホン酸リチウム0.1部及びDMF20部を配合したモノマー配合液と、2,2’−アゾビス(2,4−ジメチルバレロニトリル)0.6部及び2,2’−アゾビス(2−メチルブチロニトリル)1.2部をDMF10部に溶解した開始剤溶液とを4つ口フラスコ内に窒素を吹き込みながら、撹拌下、滴下ロートで2時間かけて連続的に滴下してラジカル重合を行った。滴下終了後、80℃に昇温し反応を5時間継続し樹脂濃度50%の共重合体溶液を得た。これにDMF133.3部を加えて室温まで冷却し樹脂濃度30重量%の被覆用樹脂溶液を得た。
LiNi0.8Co0.15Al0.05O2粉末96部を万能混合機に入れ、室温、150rpmで撹拌した状態に、樹脂の固形分が2部になる量に秤量した製造例1で得られた被覆用樹脂溶液(樹脂濃度30重量%)を60分かけて滴下混合し、更に30分撹拌した。
難黒鉛化性炭素[商品名「カーボトロン(登録商標)PS(F)」、株式会社クレハ・バッテリー・マテリアルズ・ジャパン製]90部を万能混合機に入れ、室温、150rpmで撹拌した状態に、樹脂の固形分が5部になる量に秤量した製造例1で得られた被覆用樹脂溶液(樹脂濃度30重量%)を60分かけて滴下混合し、更に30分撹拌した。
エチレンカーボネート(EC)とプロピレンカーボネート(PC)の混合溶媒(体積比率1:1)に、0.5重量%の1,3−プロパンスルトン(PS)を加えた後、LiPF6を1mol/Lの割合で溶解させてリチウムイオン電池用電解液を作製した。
実施例で用いられる集電体は、以下のようにして作製した。
二軸押出機にて、ポリプロピレン(PP)[商品名「サンアロマー(登録商標)PL500A」、サンアロマー株式会社製]75重量%、アセチレンブラック[商品名「デンカブラックHS−100」]20重量%、及び樹脂改質剤[商品名「ユーメックス(登録商標)1001」、三洋化成工業株式会社製]5重量%を、180℃、100rpm、滞留時間10分の条件で溶融混練し集電体用材料を得た。なお、上記各成分の量は混合比を表わし、ポリプロピレン、アセチレンブラック及び樹脂改質剤の合計が100重量%である。得られた集電体用材料を、熱プレス機により圧延することで、厚さ100μmの集電体1を得た。
液状エポキシ樹脂[商品名「セロキサイド(登録商標)2021P」、株式会社ダイセル製、脂環式エポキシ樹脂]7部、多官能エポキシ樹脂[商品名「マープルーフ(登録商標)G2050M」、日油株式会社製]15部、メチルエチルケトン75部、アセチレンブラック(商品名「デンカブラックHS−100」)3部及びエポキシ樹脂用硬化剤(商品名「サンエイドSI−60」、三新化学工業株式会社製)0.5部を混合して高分子材料含有導電性部材形成用の導電性部材用インキ1を調製した。
液状エポキシ樹脂(商品名「セロキサイド2021P」)7部、多官能エポキシ樹脂(商品名「マープルーフG2050M」)15部、メチルエチルケトン75部、ニッケルフィラー(商品名「T255」、日興リカ株式会社製、一次粒子の標準粒子径:2.2〜2.8μm)3部及び硬化剤(商品名「サンエイドSI−60」)0.5部を混合して高分子材料含有導電性部材形成用の導電性部材用インキ2を調製した。
炭素繊維は、Eiichi Yasuda,Asao Oya,Shinya Komura,Shigeki Tomonoh,Takashi Nishizawa,Shinsuke Nagata,Takashi Akatsu、CARBON、50、2012、1432−1434及びEiichi Yasuda,Takashi Akatsu,Yasuhiro Tanabe,Kazumasa Nakamura,Yasuto Hoshikawa,Naoya Miyajima、TANSO、255、2012、254〜265頁の製造方法を参考にして作製した。
製造例2で得られた被覆正極活物質粒子98部、製造例6で得られた炭素繊維2部及び製造例4で得られた電解液70部を混合し、更に自転公転ミキサー(株式会社シンキー製あわとり練太郎)にて2000rpmで5分間混練し、被覆正極活物質組成物を作製した。長さ100mm×幅100mmのアラミド不織布(型番2486R、日本バイリーン株式会社製、[厚さ20μm])上に長さ50mm×幅50mmの開口部を有するマスクを重ね、前記被覆正極活物質組成物をスキージで開口部内に塗工し、長さ50mm×幅50mm、厚み約1mmの被覆正極活物質層を形成した。
製造例3で得られた被覆負極活物質粒子98部、製造例6で得られた炭素繊維2部及び製造例4で得られた電解液150部を前記正極の調整と同様に混合、混練して被覆負極活物質組成物を作製した。長さ100mm×幅100mmに切断したアラミド不織布上に長さ55mm×幅55mmの開口部を有するマスクを重ね、前記被覆負極活物質組成物をスキージで開口部内に塗工し、長さ55mm×幅55mm、厚み約1mmの被覆負極活物質層を形成した。
LiNi0.8Co0.15Al0.05O2粉末90部、アセチレンブラック[商品名「デンカブラックHS−100」]10部、ポリフッ化ビニリデン[シグマアルドリッチ社製]5部、N−メチルピロリドン30部を加え、乳鉢で充分に混合し比較用正極活物質組成物を得た。得られた比較用正極活物質組成物を、厚さ20μmのアルミニウム電解箔上の片面に塗布し、100℃で15分間乾燥させた後、更に減圧下(1.3kPa)、80℃で8時間乾燥して、比較用正極を作製した。乾燥後の電極厚さはアルミ箔を含めて620μmであった。
黒鉛粉末[日本黒鉛工業株式会社製]90部、アセチレンブラック(商品名「デンカブラックHS−100」)5部、カルボキシメチルセルロースナトリウム塩[商品名「セロゲン(登録商標)F−BSH4」、第一工業製薬株式会社製]2.5部、SBR(スチレン−ブタジエンゴム)エマルション(JSR株式会社製、樹脂濃度40重量%)6.25部、水30部を加え、遊星ミルで充分に混合し、比較用負極活物質組成物を得た。得られた比較用負極活物質組成物を、厚さ20μmの銅箔の片面に塗布し、常圧で80℃/3時間乾燥後、真空乾燥を80℃/8時間行って溶媒を蒸発させ、比較用負極を作製した。乾燥後の電極厚さは銅箔を含めて720μmであった。
(本発明のリチウムイオン電池及び比較用電池の作製)
製造例7及び製造例8で得られたリチウムイオン二次電池用電極同士、並びに比較製造例1及び比較製造例2で得られた比較用電極同士をそれぞれ組み合わせ、以下の方法で本発明のリチウムイオン電池及び比較用電池を作製した。
作製した本発明のリチウムイオン電池を2枚の厚さ約1mmのブリキ板の間に挟み、0.2MPaの圧力をかけた。室温下、充放電測定装置「バッテリーアナライザー1470型」[東陽テクニカ株式会社製]を用いて、0.05Cの電流で電圧4.3Vまで充電し、10分間の休止後、0.05Cの電流で電圧2.5Vまで放電して1回目の充放電を行った。続いて電池を挟んでいたブリキ板を外し、1回目の充放電と同様に電圧4.3Vまで充電し、10分間の休止後に電圧2.5Vまでの放電を行い、このときの電池容量を測定した。本発明のリチウムイオン電池について得られた電池容量を正電の表面積で割ることで算出した単位面積当たりの容量(放電容量)は20mAh/cm2であった。比較用電池についてもブリキ板に挟まないこと以外は本発明のリチウムイオン電池と同様に充放電を行い、2回目の充放電での電池容量から放電容量を計算した。比較用電池の放電容量は4mAh/cm2であった。
放電容量の測定を行った本発明のリチウムイオン電池及び比較用電池のそれぞれをJISK5600−5−1:1999 第5部−第1節 耐屈曲性(円筒形マンドレル法)に記載の円筒形治具に準拠した直径20mmの円筒形治具に巻き付けた後に再び平らに戻すという操作を10回繰り返した。次いで本発明のリチウムイオン電池及び比較用電池を十字の折り目が付くように2方向に同時に折り曲げ、折り曲げた状態を維持したままLEDを接続した。実施例で作成した本発明のリチウムイオン電池のみLEDが点灯し、比較用電池に接続したLEDは点灯しなかった。
1 発電部
2 正極
3 負極
4 セパレータ
5 正極活物質層
6 負極活物質層
7 正極集電体
8 負極集電体
9 シール部材
11 正極活物質粒子
12 負極活物質粒子
15 基材
16 第1の導電層
17 第2の導電層
18 第3の導電層
19 導電層
20 電池外装容器
21 積層発電部
Claims (9)
- 正極集電体、正極活物質層、セパレータ、負極活物質層及び負極集電体を順に積層した単電池を備える発電部と前記発電部を収容する電池外装容器とを有してなるリチウムイオン電池であって、
前記正極活物質層が正極活物質粒子の非結着体であり、前記負極活物質層が負極活物質粒子の非結着体であり、
前記単電池が可撓性を有するリチウムイオン電池。 - 請求項1に記載のリチウムイオン電池において、
前記電池外装容器が可撓性を有するリチウムイオン電池。 - 請求項1に記載のリチウムイオン電池において、
前記正極集電体及び前記負極集電体が導電性樹脂層を有する集電体であるリチウムイオン電池。 - 請求項1に記載のリチウムイオン電池において、
前記正極活物質層及び/又は前記負極活物質層の厚さが200μm以上であるリチウムイオン電池。 - 請求項1に記載のリチウムイオン電池において、
正極活物質層が前記正極活物質粒子の表面の少なくとも一部が導電助剤と被覆用樹脂とを含んでなる被覆剤で被覆されている被覆正極活物質粒子を含み、
負極活物質層が前記負極活物質粒子の表面の少なくとも一部が被覆用樹脂を含んでなる層で被覆されている被覆負極活物質粒子を含むリチウムイオン電池。 - 請求項1に記載のリチウムイオン電池において、
前記正極活物質層及び前記負極活物質層は繊維状導電性フィラーを含むリチウムイオン電池。 - 請求項1に記載のリチウムイオン電池において、
前記正極集電体は前記正極活物質層を積層する面に第1の導電層を有し、
前記負極集電体は前記負極活物質層を積層する面に第2の導電層を有するリチウムイオン電池。 - 請求項1に記載のリチウムイオン電池において、
前記発電部の最外表側に第3の導電層を有するリチウムイオン電池。 - 請求項1に記載のリチウムイオン電池において、
前記発電部が2つ以上の単電池を積層した積層発電部であるリチウムイオン電池。
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