JP2023018616A - リチウムイオン電池電極の製造方法と製造装置 - Google Patents
リチウムイオン電池電極の製造方法と製造装置 Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 142
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- 239000000758 substrate Substances 0.000 claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 60
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 60
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 239000007772 electrode material Substances 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000005507 spraying Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000007921 spray Substances 0.000 claims description 53
- 238000011084 recovery Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 238000007790 scraping Methods 0.000 claims description 3
- 239000011149 active material Substances 0.000 abstract description 15
- 230000000052 comparative effect Effects 0.000 description 38
- 230000001351 cycling effect Effects 0.000 description 17
- 238000010586 diagram Methods 0.000 description 16
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002238 carbon nanotube film Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910011279 LiCoPO4 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910014858 LiMn2PO4 Inorganic materials 0.000 description 1
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910015915 LiNi0.8Co0.2O2 Inorganic materials 0.000 description 1
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002079 double walled nanotube Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical compound [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M10/052—Li-accumulators
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- H01M4/139—Processes of manufacture
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Abstract
Description
ステップ(S1)、カーボンナノチューブ原料を製造する。
ステップ(S2)、リチウムイオン電池の電極活物質および溶媒を提供する。
ステップ(S3)、カーボンナノチューブ原料及び電極活物質を溶媒と混合し、超音波分散させて、電極混合物を形成する。
ステップ(S4)、電極混合物を基板に噴霧して電極層を形成し、電極層を乾燥させた後、基板を除去してリチウムイオン電池電極を形成する。
ステップ(S41)、電極混合物を回収装置16に入れる。
ステップ(S42)、液体パイプ106を回収装置16に設置し、スプレーガンの位置を固定する。
ステップ(S43)、回転装置18を始動して基板12を回転させ、スプレーガン10を使用して基板12の表面に電極混合物を噴霧して電極層を形成する。
ステップ(S44)、電極層を乾燥させた後、基板12を取り外してリチウムイオン電池電極20を得る。
0.2gの超配列カーボンナノチューブ及び1gのリン酸鉄リチウム(LEP)粉末を600mLのエタノールに入れ、30分間超音波分散させて電極混合物を得る。得られた電極混合物を、スプレーガンを介して1000メッシュのフィルタースクリーンに噴霧し、乾燥後、自立構造を有するリチウムイオン電池正極をフィルタースクリーンから取り外す。
活物質であるリン酸鉄リチウム、導電剤super-p(導電性カーボンブラック)及びバインダー(PVDF)を質量比8:1:1で混合し、NMP溶剤に分散させてスラリーを得る。金属集電体(AlまたはCu)にスラリーをコーティングして乾燥させた後、リチウムイオン電池の正極が得られる。
実施例1のリチウムイオン電池の正極を正極とし、ポリプロピレンフィルムをセパレータとし、リチウム箔を負極とし、ステンレスガスケットを使用して、前記の部品が積層され、R2016バッテリーシェルによって組み立ち、ボタン電池を形成する。FECとFEMCとHFEとからなる混合液に1MのLiPF6を添加し、電解質を形成する。FECとFEMCとHFEとの質量パーセント比は2:6:2である。ボタン電池の組み立て工程は、アルゴングローブボックスで行わる。
比較例2のボタン電池の構造は、実施例2のボタン電池の構造と基本的に同じである。異なる点は、比較例1のリチウムイオン電池の正極を正極として使用することである。
0.2gの超配列カーボンナノチューブ及び1gのNCA粉末を600mLのエタノールに30分間超音波分散させて電極混合物を得る。得られた電極混合物を、スプレーガンを介して1000メッシュのフィルタースクリーンに噴霧し、乾燥後、自立構造を有するリチウムイオン電池正極をフィルタースクリーンから取り外す。上記のリチウムイオン電池正極を正極とし、ポリプロピレンフィルムをセパレータとし、リチウム箔を負極とし、ステンレスのガスケットを使用し、前記の部品が積層され、R2016バッテリーシェルによって組み立ち、ボタン電池を形成する。FECとFEMCとHFEとからなる混合液に1MのLiPF6を添加し、電解質を形成する。FECとFEMCとHFEとの質量パーセント比は2:6:2である。ボタン電池の組み立て工程は、アルゴングローブボックスで行わる。
活物質NCA、導電剤super-p(導電性カーボンブラック)、バインダー(PVDF)を質量比8:1:1で混合し、NMP溶剤に分散させてスラリーを得る。金属集電体(AlまたはCu)にスラリーをコーティングして乾燥させた後、リチウムイオン電池の正極が得られる。比較例3のボタン電池の構造は実施例3のボタン電池の構造と基本的に同じであるが、異なる点は比較例3のリチウムイオン電池の正極を正極として使用する。
10 スプレーガン
102 気体入口
104 液体入口
106 液体パイプ
108 気体パイプ
12 基板
14 支持体
16 回収装置
162 溝
18 回転装置
20 リチウムイオン電池電極
Claims (5)
- カーボンナノチューブ原料を製造する第一ステップと、
リチウムイオン電池の電極活物質および溶媒を提供する第二ステップと、
前記カーボンナノチューブ原料及び前記電極活物質を前記溶媒と混合し、超音波分散させて、電極混合物を形成する第三ステップと、
前記電極混合物を基板に噴霧して電極層を形成し、前記電極層を乾燥させた後、前記基板を除去して、リチウムイオン電池電極を形成する第四ステップと、
を含むことを特徴とするリチウムイオン電池電極の製造方法。 - 前記カーボンナノチューブ原料の製造方法は、基板に超配列カーボンナノチューブアレイを成長するサッブステップと、基板から超配列カーボンナノチューブアレイを削り取って前記カーボンナノチューブ原料を得るサッブステップと、を含むことを特徴とする、請求項1に記載のリチウムイオン電池電極の製造方法。
- 前記電極活物質は、リチウムイオン電池の正極活物質またはリチウムイオン電池の負極活物質であることを特徴とする、請求項1に記載のリチウムイオン電池電極の製造方法。
- 前記第四ステップは、
前記電極混合物を回収装置に入れる第一サッブステップと、
液体パイプを前記回収装置に設置し、スプレーガンの位置を固定する第二サッブステップと、
回転装置を始動して前記基板を回転させ、前記スプレーガンを使用して前記基板の表面に前記電極混合物を噴霧して前記電極層を形成する第三サッブステップと、
前記電極層を乾燥させた後、前記基板を取り外して前記リチウムイオン電池電極を得る第四サッブステップと、
を含むことを特徴とする、請求項1に記載のリチウムイオン電池電極の製造方法。 - 回転装置と、回収装置と、基板と、スプレーガンと、を含むリチウムイオン電池電極の製造装置であって、
前記回転装置は、動作時に回転軸を中心に回転され、
前記回収装置は前記回転装置に固定され、
前記基板は前記回収装置の内部に固定され、
前記スプレーガンは、前記基板の上方向に設置され、前記基板に電極混合物を噴霧することに使用されることを特徴とするリチウムイオン電池電極の製造装置。
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