JP5531347B2 - 自己支持形金属硫化物系2次元ナノ構造体の負極活物質及びその製造方法 - Google Patents
自己支持形金属硫化物系2次元ナノ構造体の負極活物質及びその製造方法 Download PDFInfo
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- 239000007773 negative electrode material Substances 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- 239000002086 nanomaterial Substances 0.000 title claims description 31
- 229910052976 metal sulfide Inorganic materials 0.000 title description 9
- 238000000034 method Methods 0.000 claims description 45
- 239000000758 substrate Substances 0.000 claims description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 28
- 229910001416 lithium ion Inorganic materials 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 22
- 206010040844 Skin exfoliation Diseases 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 239000010935 stainless steel Substances 0.000 claims description 18
- 229910001220 stainless steel Inorganic materials 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000004549 pulsed laser deposition Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002135 nanosheet Substances 0.000 description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 239000010409 thin film Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 229910052744 lithium Inorganic materials 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 13
- 239000011149 active material Substances 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 239000010453 quartz Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 229910000733 Li alloy Inorganic materials 0.000 description 7
- 239000001989 lithium alloy Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
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- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910021383 artificial graphite Inorganic materials 0.000 description 4
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- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
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- 229910021384 soft carbon Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical group 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910018091 Li 2 S Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
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- 239000007774 positive electrode material Substances 0.000 description 2
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920006370 Kynar Polymers 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910008365 Li-Sn Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910006759 Li—Sn Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
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- 229910021469 graphitizable carbon Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- -1 nickel metal hydride Chemical class 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3485—Sputtering using pulsed power to the target
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5873—Removal of material
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
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- H01L31/0264—Inorganic materials
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
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Description
また、本発明は、上記負極活物質を製造する方法を提供することにその目的がある。
また、本発明は、上記負極活物質を含む負極を提供することにその目的がある。
また、本発明は、上記負極活物質を採用する2次電池を提供することにその目的がある。
特定方向に向けて弱い結合力を帯びる層状構造を有する、スズ硫化物(Sn S)粉末を秤量してモールドに入れた後、一軸圧力を加えて仮凝集体を成形し、前記仮凝集体を水素雰囲気下で580〜600°Cで3〜5時間熱処理して、錫硫化物系物質からなる凝集体を製造するステップと、
前記製造した凝集体をパルスレーザー蒸着用電気炉内のチューブに挿入装着するステップと、
前記チューブ内に金属基板を挿入し、所望の形状が得られるように、前記凝集体から所定の距離だけ離れて位置させるステップと、
前記チューブ内の圧力を真空状態に下げ、前記電気炉の温度を590〜610°Cに上げるステップと、
前記チューブ内に、前記金属基板に到達するスズ硫化粒子が適切な量となる、エネルギー密度、剥離速度、剥離回数および剥離時間のパルスレーザーを注入して前記凝集体を剥離するステップと、
を含み、
前記錫硫化物系物質を前記金属基板上に2次元ナノ構造体として直接成長させることを特徴とする、自己支持型錫硫化物系2次元ナノ構造体のリチウムイオン二次電池用負極活物質の製造方法が提供される。
ツヤのある暗い灰色のSnSパウダー2gを秤量して直径1cmの円柱状モールドに均一に注入した後、600psiの圧力で一軸成形して凝集体を製造した。
パルスレーザー蒸着前にレーザーのフォーカシング作業が必要であるため、レーザーが注入される部分に焦点距離(focal length)50cmの焦点レンズを位置させた。レーザーが適切な大きさでフォーカシングされたか否かを印画紙により確認し、パルスレーザー蒸着用電気炉の内部に直径28cm、長さ80cmの石英チューブを挿入した。
上記実施例1〜2により製造された自己支持形SnS2次元ナノシートの2次電池用負極活物質としての電気化学的特性を評価し、その特性を薄膜及びパウダー電極と比較するために下記のように半電池を製造した。
上記実施例1〜2により製造されたSnSナノシートと、その対照群であるSnS薄膜はそれ自体を電極として使用した。
自己支持形SnS2次元ナノシートの電気化学的特性を測定するために、リチウム金属を負極とし、上記(a)で製造した電極を正極とした。この2つの間に電解質と分離膜(Celgard2400)を入れてスウェージロック(Swagelok)型の半電池を構成した。この時、エチレンカーボネイト(EC)とジメチルカーボネイト(DMC)が体積比1:1で混ぜられた溶液に、LiPF6が溶解された物質を電解質として使用した。上記製造過程は、不活性気体であるアルゴンで充填されているグローブボックス(glove box)の中で行った。
Claims (8)
- 自己支持型錫硫化物系2次元ナノ構造体のリチウムイオン二次電池用負極活物質を製造する方法であって、
特定方向に向けて弱い結合力を帯びる層状構造を有する、スズ硫化物(Sn S)粉末を秤量してモールドに入れた後、一軸圧力を加えて仮凝集体を成形し、前記仮凝集体を水素雰囲気下で580〜600°Cで3〜5時間熱処理して、錫硫化物系物質からなる凝集体を製造するステップと、
前記製造した凝集体をパルスレーザー蒸着用電気炉内のチューブに挿入装着するステップと、
前記チューブ内に金属基板を挿入し、所望の形状が得られるように、前記凝集体から所定の距離だけ離れて位置させるステップと、
前記チューブ内の圧力を真空状態に下げ、前記電気炉の温度を590〜610°Cに上げるステップと、
前記チューブ内に、前記金属基板に到達するスズ硫化粒子が適切な量となる、エネルギー密度、剥離速度、剥離回数および剥離時間のパルスレーザーを注入して前記凝集体を剥離するステップと、
を含み、
前記錫硫化物系物質を前記金属基板上に2次元ナノ構造体として直接成長させることを特徴とする、
自己支持型錫硫化物系2次元ナノ構造体のリチウムイオン二次電池用負極活物質の製造方法。 - 前記金属基板は、前記凝集体の中心から14〜20cm離れた所に位置することを特徴とする、
請求項1に記載のリチウムイオン二次電池用負極活物質の製造方法。 - 前記金属基板が凝集体から離れるほど、ナノ構造体の厚さが薄く合成されることを特徴とする、
請求項1または2に記載のリチウムイオン二次電池用負極活物質の製造方法。 - 前記凝集体を剥離するステップにおいて、
パルスレーザーのエネルギ密度を0.8〜1J/cm2に設定し、
前記凝集体を1秒当たり3〜5回の剥離速度で、25〜35分間剥離する、
ことを特徴とする、
請求項1に記載のリチウムイオン二次電池用負極活物質の製造方法。 - 前記凝集体の高さを調節してフォーカシングしたレーザーが前記凝集体の中心に到達するようにすることを特徴とする、
請求項1に記載のリチウムイオン二次電池用負極活物質の製造方法。 - 前記金属基板は、触媒がコーティングされていないステンレススチール(SUS)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二次電池用負極活物質の製造方法。 - 前記2次元ナノ構造体を10〜15nmの厚さで合成することを特徴とする、
請求項1に記載のリチウムイオン二次電池用負極活物質の製造方法。 - 前記2次元ナノ構造体を2×2cm2以下の大きさで合成することを特徴とする、
請求項1に記載のリチウムイオン二次電池用負極活物質の製造方法。
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