JP6037472B2 - リチウム蓄電池 - Google Patents
リチウム蓄電池 Download PDFInfo
- Publication number
- JP6037472B2 JP6037472B2 JP2014518019A JP2014518019A JP6037472B2 JP 6037472 B2 JP6037472 B2 JP 6037472B2 JP 2014518019 A JP2014518019 A JP 2014518019A JP 2014518019 A JP2014518019 A JP 2014518019A JP 6037472 B2 JP6037472 B2 JP 6037472B2
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- JP
- Japan
- Prior art keywords
- storage battery
- current collector
- lithium
- active material
- 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.)
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- 238000003860 storage Methods 0.000 title claims description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 32
- 229910052744 lithium Inorganic materials 0.000 title claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000011149 active material Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011244 liquid electrolyte Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- 229910010293 ceramic material Inorganic materials 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 150000001247 metal acetylides Chemical class 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 239000002121 nanofiber Substances 0.000 claims 1
- 150000004767 nitrides Chemical class 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910012733 LiCo1/3Mn1/3Ni1/3O2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910004786 P-Li Inorganic materials 0.000 description 1
- 229910004796 P—Li Inorganic materials 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZWOYKDSPPQPUTC-UHFFFAOYSA-N dimethyl carbonate;1,3-dioxolan-2-one Chemical compound COC(=O)OC.O=C1OCCO1 ZWOYKDSPPQPUTC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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Description
本発明の主たる目的は、電子伝導性要素と活物質からなる圧縮された3D電極の前述の優位性を包含するリチウム蓄電池を提供することであり、その3D電極は一方で蓄電池セルの大きな容量を維持しながら放電充電時間が短縮されるという優位性を有する。本発明の他の目的は、電極の圧縮または圧延による効率的な生産を可能にする電極の構造を提供することである。
(技術的解決方法)
本発明の目的は以下のリチウム蓄電池により達成され、またそれにより前述の欠点は解消される:容器をもつリチウム蓄電池であって、少なくとも1つのセルを有し、そのセルは、セパレータによって分離される2つの電極と、集電器と、そして有機溶媒中のリチウム塩の溶液から構成される液体電解質と、を有するリチウム蓄電池において、有機結合剤の無いそれぞれの電極が金属製の網、エキスパンドメタルまたは多孔金属箔の形状での多孔性の細長い金属板から形成される集電器の両側の上に押圧される、ことを特徴とするリチウム蓄電池。
既存技術と異なり、個々の電極またはセルは結合剤により箔の上に取り付けられない。電極は直接、そして有機結合剤無しに、集電器の多孔性の細長い金属板の開口の中にフレームのシステムを用いずに押圧される。
セルは相互にボルトにより接続される2つの端末カバーの間で締め付けられる。
このような材料は好適には、リチウムのインターカーレートプロセスを数秒に短縮する可能性のあるナノ寸法の粒子として存在する。
(有利な効果)
本発明に基づくセパレータの優位点は、その総合的熱安定性と有機結合剤のない電極材料が大幅に低い電気抵抗を有し、そして蓄電池の充放電プロセスにおいて放熱量が有意に少ないという事実に基づく安全性である。有機結合剤が無いことは電極の内部形態と共に、リチウムイオンの電極内での高い移動性を提供する。ここに記載された電極構成と材料組成は、従来のセパレータが使用された場合でも充電器の短縮された充放電時間と高い容積容量の獲得を可能にする。
(実施例1)
図1に概略的断面図として示された蓄電池は、容器10を有し、その中に個々の蓄電池セルが端部カバー1a,1bの間に互いに積み重なって配置される。蓄電池セルは一緒にボルト11で締め付けられる。各セルは1つの正電極2a、1つの負電極2bおよびそれら電極間に位置するセパレータ4から構成される。各正電極2aは集電器3aの中に押圧され、そして各負電極2bは集電器3bの中に押圧される。有機結合剤のない各電極の材料は集電器にフレームなしで、しかしいくらかのオーバーハングを有して押圧され、それにより電極は集電器表面の上および下に伸長し、ここで対向する外部電極面の間の最小距離は集電器3a、3bの厚みの少なくとも3倍に等しい。
リチウム蓄電池はセパレータ4で互いに分離される13個の負電極2bと14個の正電極2aからなる。各電極は2x25mmの広さと0.3−0.35mmの厚みを持つ。正電極は重量比80%の約200nmのLFP粒子からなる典型的に寸法2μm以下の小集団の形態を有するLiFePO4(Life Power(登録商標)−P2(LFP))および重量比10%の電子伝導性カーボンおよび重量比10%の圧縮時に結合特性を持つ導電性圧縮性カーボンから構成される。Ketjen Black EC−300Jの商品名で市販されるこのタイプのカーボンは、比表面積800m2/g、比空隙容積310−345ml/100g、殆ど150nm超の団粒寸法、および密度125−145kg/m3を有する。あるいは商品名EC−600JD,EC−330JMAで販売されるカーボンを使用してもよい。カーボンは厚さ0.04mm、最大孔寸法「a」が1.3mmのアルミエキスパンドメタル集電器の上に約25kN/cm2の圧力で圧迫される。代替として、商品名EC−600JD,EC−330JMAが使用された。
リチウム蓄電池がセパレータ4で分離された12個の負電極2bと13個の正電極2aで構成される。セパレータはセラミックパウダーAl2O3と80μmの厚みのグラスファイバーとの混合物から調製された。正電極の活物質はLiCo1/3Mn1/3Ni1/3O2(NMC)であり、負電極の活物質はナノ粒子形態のLi4Ti5O12(LTS)であった。各電極の広さは2x25mmであり、その厚さは0.3−0.35mmであった。蓄電池モジュールの容積は3.25cm3であり、規定容量は162Wh/リットルであった。
本発明の蓄電池は100℃以上の高温で動作可能なリチウム蓄電池の生産に使用可能である。この蓄電池は今日の高電圧システムを伴う鉛−酸蓄電池の代替、即ち自動車、手持ち電動工具、そして携帯型電気および電子製品および装置用に適している。
Claims (6)
- 容器を有し、フレームを有しないリチウム蓄電池であって、少なくとも1つのセルを有し、
前記セルは、
有機結合剤を含まない2つの電極(2a,2b)を有し、
金属線の網、エキスパンドメタルまたは多孔金属箔の形状での多孔性の細長い金属板である集電器(3a,3b)を有し、
ここにおいて第1の前記集電器(3a)と第2の前記集電器(3b)はそれぞれ第1の側と当該第1の側と反対側の第2の側とを有し、そして
セパレータ(4)と、
有機溶媒中のリチウム塩の溶液から構成される液体電解質と、
を有し、
正の電極(2a)は空間的に分散配置され、活物質と混合された電子伝導性要素を有し、そして前記活物質は最大壁厚10μmの中空球面の形態を持つかまたは最大寸法30μmの集合体または団粒の形態を持ち、かつ空隙率25−95%を有し、
前記正の電極(2a)は活物質と電子伝導性要素の混合物からなり、有機結合剤を含まず、前記多孔性の細長い金属板の開口部の中に前記第1の集電器(3a)の前記第1の側と前記第2の側の両側から直接押圧され、そして
負の電極(2b)は活物質と電子伝導性要素の混合物からなり、前記活物質は黒鉛、リチウムチタン酸化物またはリチウムに対する電位が前記正の電極より低い材料からなる材料のグループから選択され、そして、前記活物質と電子伝導性要素の混合物を有する、有機結合剤を含まない前記負の電極(2b)は、前記多孔性の細長い金属板の開口部の中に前記第2の集電器(3b)の前記第1の側と前記第2の側の両側から直接押圧され、
前記集電器(3a,3b)の上の前記電極(2a,2b)の前記第1の側の部分および前記第2の側の部分のそれぞれの最小厚みは、前記集電器(3a,3b)の厚みの3倍であり、
前記集電器(3a,3b)の厚さは30−500μmである、
ことを特徴とするフレームを有しないリチウム蓄電池。 - 前記セルが、相互にボルト(11)により接続される2つの端末カバー(1a,1b)の間で締め付けられる、ことを特徴とする請求項1に記載のフレームを有しないリチウム蓄電池。
- 前記集電器(3a,3b)は、前記集電器(3a,3b)の1つの端部に突起(31)を備える、ことを特徴とする請求項1に記載のフレームを有しないリチウム蓄電池。
- 前記電子伝導性要素は導電性カーボン、導電性金属、電気的に伝導性の酸化物、金属炭化物および窒化物からなるグループから選択される、ことを特徴とする請求項1に記載のフレームを有しないリチウム蓄電池。
- 前記活物質はリチウム、マンガン、クロム、バナジウム、チタン、コバルト、アルミニウム、ニッケル、鉄、ランタン、ニオブ、ホウ素、セリウム、タンタル、スズ、マグネシウム、イットリウムおよびジルコニウムのグループから選択された1つまたはそれ以上の要素の酸化物またはリン酸塩の化合物である、ことを特徴とする請求項1に記載のフレームを有しないリチウム蓄電池。
- 前記セパレータはナノ繊維、繊維の形態での圧縮された無機セラミック材料、Al2O3,SiO2,ガラス、またはZrO2 、または有機多孔箔からなる材料のグループから選択される、ことを特徴とする請求項1に記載のフレームを有しないリチウム蓄電池。
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JP4927064B2 (ja) * | 2008-11-11 | 2012-05-09 | シャープ株式会社 | 二次電池 |
CN101911369A (zh) * | 2008-12-01 | 2010-12-08 | 丰田自动车株式会社 | 固体电解质电池、车辆、电池搭载设备和固体电解质电池的制造方法 |
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HRP20181922T1 (hr) | 2019-01-11 |
MX351663B (es) | 2017-10-18 |
RU2014102662A (ru) | 2015-08-10 |
CY1120966T1 (el) | 2019-12-11 |
KR20140058508A (ko) | 2014-05-14 |
CL2013003703A1 (es) | 2014-10-03 |
PT2727171T (pt) | 2018-12-14 |
CZ2011405A3 (cs) | 2013-01-09 |
PL2727171T3 (pl) | 2019-03-29 |
JP2015502626A (ja) | 2015-01-22 |
EP2727171B1 (en) | 2018-09-05 |
CA2840547A1 (en) | 2013-01-10 |
SI2727171T1 (sl) | 2019-01-31 |
RU2594010C2 (ru) | 2016-08-10 |
HUE040250T2 (hu) | 2019-02-28 |
CA2840547C (en) | 2018-09-04 |
AU2012279986A1 (en) | 2014-01-23 |
BR112013033882B1 (pt) | 2021-07-06 |
AU2012279986B2 (en) | 2016-12-22 |
US9401510B2 (en) | 2016-07-26 |
ES2699528T3 (es) | 2019-02-11 |
WO2013005135A1 (en) | 2013-01-10 |
CN103828090A (zh) | 2014-05-28 |
DK2727171T3 (en) | 2018-12-10 |
US20150086848A1 (en) | 2015-03-26 |
IN2014MN00019A (ja) | 2015-06-12 |
BR112013033882A2 (pt) | 2017-02-14 |
RS58181B1 (sr) | 2019-03-29 |
MX2014000122A (es) | 2014-06-23 |
CN103828090B (zh) | 2016-06-29 |
LT2727171T (lt) | 2018-12-27 |
KR101979040B1 (ko) | 2019-05-15 |
EP2727171A1 (en) | 2014-05-07 |
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