JP2023515605A - 負極活物質、その製造方法、及び該負極活物質を備えるリチウム二次電池 - Google Patents
負極活物質、その製造方法、及び該負極活物質を備えるリチウム二次電池 Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 77
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 74
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 100
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000011247 coating layer Substances 0.000 claims abstract description 61
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 60
- 239000002245 particle Substances 0.000 claims abstract description 40
- 238000003486 chemical etching Methods 0.000 claims abstract description 8
- 239000012621 metal-organic framework Substances 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 25
- 150000002736 metal compounds Chemical class 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 150000002894 organic compounds Chemical class 0.000 claims description 19
- 229910052725 zinc Inorganic materials 0.000 claims description 17
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 16
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 239000004246 zinc acetate Substances 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- -1 carboxylic acid compound Chemical class 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 230000006866 deterioration Effects 0.000 abstract description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract 1
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- 239000007864 aqueous solution Substances 0.000 description 13
- 229910002804 graphite Inorganic materials 0.000 description 12
- 239000010439 graphite Substances 0.000 description 12
- 229910021383 artificial graphite Inorganic materials 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000007833 carbon precursor Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
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- 238000004626 scanning electron microscopy Methods 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 239000002612 dispersion medium Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 239000011357 graphitized carbon fiber Substances 0.000 description 1
- 239000002946 graphitized mesocarbon microbead Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
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- 230000016507 interphase Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
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Abstract
Description
炭素系材料と、
前記炭素系材料の表面に自己結着した多孔性炭素コーティング層とを含むことを特徴とするリチウム二次電池用負極活物質が提供される。
前記多孔性炭素コーティング層がZn、Co、Cu、Ti、Hf、Zr、Ni、Mg、Ti、V、Cr、Fe、Alまたはこれらのうち2以上の金属元素を含み得る。
前記多孔性炭素コーティング層がZn、Coまたはこれらの組合せである金属元素を含み得る。
前記多孔性炭素コーティング層の含量が全体負極活物質重量対比50wt%以下であり得る。
前記炭素系材料が25μm以下の平均粒径を有し得る。
炭素系材料を用意する段階と、
前記炭素系材料の表面に金属有機構造体(Metal-Organic Frameworks、MOFとも略称する)を直接成長させる段階と、
前記MOFが成長した炭素系材料を乾燥する段階と、
前記乾燥した、MOFが成長した炭素系材料を熱処理し、前記炭素系材料の表面に金属元素を含む多孔性炭素コーティング層を形成する段階とを含むことを特徴とするリチウム二次電池用負極活物質の製造方法が提供される。
前記炭素系材料の表面に金属有機構造体(MOF)を直接成長させる段階が、
金属化合物、有機化合物、及び過酸化水素を含む前駆体溶液を前記炭素系材料に混合して前記炭素系材料の表面に金属有機構造体を直接成長させる段階を含むか、または、
前記炭素系材料が過酸化水素に分散した炭素系材料組成物に、金属化合物溶液と有機化合物溶液とを混合して前記炭素系材料の表面に金属有機構造体を直接成長させる段階を含み得る。
前記金属化合物が金属アセテート(metal acetate)、金属ナイトレート(metal nitrate)、金属カーボネート(metal carbonate)、金属ヒドロキシド(metal hydroxide)またはこれらのうち2以上を含み得る。
前記金属化合物の金属がZn、Co、Cu、Ti、Hf、Zr、Ni、Mg、Ti、V、Cr、Fe、Alまたはこれらのうち2以上を含み得る。
前記金属化合物の金属がZn、Coまたはこれらの組合せであり得る。
前記有機化合物がカルボン酸化合物、イミダゾール化合物またはこれらのうち2以上を含み得る。
前記金属化合物が酢酸亜鉛(zinc acetate)、酢酸コバルト(cobalt acetate)またはこれらの混合物であり、前記有機化合物が2-メチルイミダゾールであり得る。
前記MOFの炭素系材料の表面への直接成長を誘導するため、前記過酸化水素が前記前駆体溶液内に1~50wt%で含まれ得る。
前記乾燥段階が25℃~120℃で行われ得る。
前記熱処理段階が800℃~1,500℃の不活性ガス雰囲気で1~10時間行われ得る。
前記多孔性炭素コーティング層を形成する段階の後に、前記金属元素を除去する化学的エッチング段階をさらに含み得る。
前記化学的エッチング段階が、0.5~3Mの酸溶液で1~10時間撹拌した後25℃~120℃で乾燥することで行われ得る。
多孔性炭素コーティング層の含量(wt%)=[(b-a)/b]×100
炭素系材料を用意する段階と、
前記炭素系材料の表面に金属有機構造体(MOF)を直接成長させる段階と、
前記MOFが成長した炭素系材料を乾燥する段階と、
前記乾燥した、MOFが成長した炭素系材料を熱処理し、前記炭素系材料の表面に金属元素を含む多孔性炭素コーティング層を形成する段階と、を含む。
<負極活物質の製造>
炭素系材料として、数平均粒径(D50)が17μmであってコーティング層が形成されていない人造黒鉛を使用した。
実施例1で製造された負極活物質を使用してリチウム二次電池を製造した。
実施例1で得られた負極活物質を1Mの塩酸溶液で化学的エッチング処理した後、100℃で乾燥して最終的に負極活物質を製造した。
負極活物質として、数平均粒径(D50)が17μmであってコーティング層が形成されていない人造黒鉛を使用した。
Claims (18)
- 炭素系材料と、
前記炭素系材料の表面に自己結着した多孔性炭素コーティング層とを含む、リチウム二次電池用負極活物質。 - 前記多孔性炭素コーティング層が、Zn、Co、Cu、Ti、Hf、Zr、Ni、Mg、Ti、V、Cr、Fe、Alまたはこれらのうち2以上の金属元素を含む、請求項1に記載のリチウム二次電池用負極活物質。
- 前記多孔性炭素コーティング層が、Zn、Coまたはこれらの組合せである金属元素を含む、請求項1または2に記載のリチウム二次電池用負極活物質。
- 前記多孔性炭素コーティング層の含量が全体負極活物質重量対比50wt%以下である、請求項1から3のいずれか一項に記載のリチウム二次電池用負極活物質。
- 前記炭素系材料が25μm以下の数平均粒径を有する、請求項1から4のいずれか一項に記載のリチウム二次電池用負極活物質。
- 請求項1から5のうちいずれか一項に記載のリチウム二次電池用負極活物質を含む負極を備える、リチウム二次電池。
- 炭素系材料を用意する段階と、
前記炭素系材料の表面に金属有機構造体(MOF)を直接成長させる段階と、
前記金属有機構造体が成長した炭素系材料を乾燥する段階と、
前記乾燥した、金属有機構造体が成長した炭素系材料を熱処理し、前記炭素系材料の表面に金属元素を含む多孔性炭素コーティング層を形成する段階とを含む、リチウム二次電池用負極活物質の製造方法。 - 前記炭素系材料の表面に金属有機構造体(MOF)を直接成長させる段階が、
金属化合物、有機化合物、及び過酸化水素を含む前駆体溶液を前記炭素系材料に混合して前記炭素系材料の表面に金属有機構造体を直接成長させる段階を含むか、または、
前記炭素系材料が過酸化水素に分散した炭素系材料組成物に、金属化合物溶液と有機化合物溶液とを混合して前記炭素系材料の表面に金属有機構造体を直接成長させる段階を含む、請求項7に記載のリチウム二次電池用負極活物質の製造方法。 - 前記金属化合物が、金属アセテート、金属ナイトレート、金属カーボネート、金属ヒドロキシドまたはこれらのうち2以上を含む、請求項8に記載のリチウム二次電池用負極活物質の製造方法。
- 前記金属化合物の金属が、Zn、Co、Cu、Ti、Hf、Zr、Ni、Mg、Ti、V、Cr、Fe、Alまたはこれらのうち2以上を含む、請求項8または9に記載のリチウム二次電池用負極活物質の製造方法。
- 前記金属化合物の金属が、Zn、Coまたはこれらの組合せである、請求項8から10のいずれか一項に記載のリチウム二次電池用負極活物質の製造方法。
- 前記有機化合物が、カルボン酸化合物、イミダゾール化合物またはこれらのうち2以上を含む、請求項8から11のいずれか一項に記載のリチウム二次電池用負極活物質の製造方法。
- 前記金属化合物が酢酸亜鉛、酢酸コバルトまたはこれらの混合物であり、前記有機化合物が2-メチルイミダゾールである、請求項8から12のいずれか一項に記載のリチウム二次電池用負極活物質の製造方法。
- 前記金属有機構造体を炭素系材料の表面に直接成長させるため、前記過酸化水素が前記前駆体溶液内に1~50wt%で含まれる、請求項8から13のいずれか一項に記載のリチウム二次電池用負極活物質の製造方法。
- 前記乾燥段階が25℃~120℃で行われる、請求項7から14のいずれか一項に記載のリチウム二次電池用負極活物質の製造方法。
- 前記熱処理段階が800℃~1,500℃の不活性ガス雰囲気で1~10時間行われる、請求項7から15のいずれか一項に記載のリチウム二次電池用負極活物質の製造方法。
- 前記多孔性炭素コーティング層を形成する段階の後に、前記金属元素を除去する化学的エッチング段階をさらに含む、請求項7から16のいずれか一項に記載のリチウム二次電池用負極活物質の製造方法。
- 前記化学的エッチング段階が、0.5~3Mの酸溶液で1~10時間撹拌した後25℃~120℃で乾燥することで行われる、請求項17に記載のリチウム二次電池用負極活物質の製造方法。
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