JP4530647B2 - リチウム二次電池用負極材料、その製造方法、及びリチウム二次電池 - Google Patents
リチウム二次電池用負極材料、その製造方法、及びリチウム二次電池 Download PDFInfo
- Publication number
- JP4530647B2 JP4530647B2 JP2003386799A JP2003386799A JP4530647B2 JP 4530647 B2 JP4530647 B2 JP 4530647B2 JP 2003386799 A JP2003386799 A JP 2003386799A JP 2003386799 A JP2003386799 A JP 2003386799A JP 4530647 B2 JP4530647 B2 JP 4530647B2
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- Prior art keywords
- negative electrode
- carbon
- electrode material
- lithium secondary
- secondary battery
- 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.)
- Expired - Lifetime
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- 239000007773 negative electrode material Substances 0.000 title claims description 59
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 53
- 229910052744 lithium Inorganic materials 0.000 title claims description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 72
- 229910052799 carbon Inorganic materials 0.000 claims description 58
- 239000002245 particle Substances 0.000 claims description 55
- 239000011246 composite particle Substances 0.000 claims description 30
- 239000011247 coating layer Substances 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 16
- 229910000733 Li alloy Inorganic materials 0.000 claims description 15
- 239000001989 lithium alloy Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 238000005229 chemical vapour deposition Methods 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052752 metalloid Inorganic materials 0.000 claims description 10
- 150000002738 metalloids Chemical class 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
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- 239000000126 substance Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- -1 specifically Chemical compound 0.000 description 9
- 238000005275 alloying Methods 0.000 description 7
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- 239000003792 electrolyte Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000002427 irreversible effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
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- 239000011261 inert gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 239000007774 positive electrode material Substances 0.000 description 4
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- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
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- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- 239000006230 acetylene black Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N germanium monoxide Inorganic materials [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
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- 238000007873 sieving Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
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- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
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- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- BZHNHDOWFCBZNK-UHFFFAOYSA-N antimony lithium Chemical compound [Li].[Sb] BZHNHDOWFCBZNK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- JYPVGDJNZGAXBB-UHFFFAOYSA-N bismuth lithium Chemical compound [Li].[Bi] JYPVGDJNZGAXBB-UHFFFAOYSA-N 0.000 description 1
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- MYWGVEGHKGKUMM-UHFFFAOYSA-N carbonic acid;ethene Chemical compound C=C.C=C.OC(O)=O MYWGVEGHKGKUMM-UHFFFAOYSA-N 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
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- 239000003925 fat Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- YFKPABFAJKUPTN-UHFFFAOYSA-N germanium lithium Chemical compound [Li].[Ge] YFKPABFAJKUPTN-UHFFFAOYSA-N 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
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- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
Description
(株)島津製作所製、レーザー式回折粒度分布測定装置(SALD−200Vを用いて測定した。
日本ベル(株)製、高精度自動ガス吸着装置(BELSORB28)を用い、液体窒素温度で窒素吸着量を多点法で測定しBET法にて比表面積を算出した。
(株)島津製作所製、熱重量分析装置(TGA−50)を用い、試料を空気気流中で900℃まで昇温して炭素を燃焼させ、重量減少量から被覆炭素量を算出した。
一酸化珪素((株)高純度化学研究所製、1μm)500gに、黒鉛(中国産、10μm)粉末500gを加え、アルゴン雰囲気下で、振動ミルで12時間複合化処理した後、篩い分けにより粒径53μm以下の複合粒子を得た。この複合粒子500gを内容積1000mlのステンレス容器に挿入し、攪拌しながら、窒素気流により粒子を流動化状態とした。容器内部の空気を窒素ガスによって完全にパージした後、流動化状態を保ちながら内部温度を950℃に昇温し、更に底部よりベンゼン蒸気を導入することにより化学蒸着処理を行って、複合粒子の表面に炭素からなる被覆層を形成した。ベンゼン濃度は10モル%であった。
試料2gに、バインダーとしてPVDF0.2gのN−メチルピロリドン溶液を加え、よく混合してペースト状にした。これを銅箔に塗布し、120℃で乾燥した後、98MPaで加圧成形した。その後、直径16mmの円形に切り出して、これを160℃で2時間真空乾燥して負極を得た。
5gのLiCoO2に導電助剤のアセチレンブラックを0.3g加えて混合した後、バインダーとしてPVDF0.3gのN−メチルピロリドン溶液を加え、よく混合してペースト状にした。これをアルミ箔に塗布し、120℃で乾燥した後、98MPaで加圧成形した。その後、直径15.9mmの円形に切り出し、160℃で2時間真空乾燥し、正極を得た。
充電は、電流密度を50mA/g、及び0.4mA/cm2とし、4.1Vでカットした。
放電は、電流密度を50mA/g、及び0.4mA/cm2とし、2.5Vでカットした。
一酸化珪素((株)高純度化学研究所製、1μm)200gに、黒鉛(中国産、10μm)粉末500gを加え、アルゴン雰囲気下で、振動ミルで12時間複合化処理した後、篩い分けにより粒径53μm以下の複合粒子を得た。この複合粒子500gを用いて、実施例1と同様に化学蒸着処理を行った。また、得られた負極材料を用いて、実施例1と同様に電池性能の評価を行った。結果を、表1及び表2に示す。
表2に示すように、この電池はサイクル性能が高く、300サイクルまで劣化はなかった。
酸化ゲルマニウム((株)高純度化学研究所製、1μm)500gに、黒鉛(中国産、10μm)粉末500gを加え、アルゴン雰囲気下で、振動ミルで12時間複合化処理した後、篩い分けにより53μm以下の複合粒子を得た。この複合粒子500gを用いて、実施例1と同様に化学蒸着処理を行った。また、得られた負極材料を用いて、実施例1と同様に電池性能の評価を行った。結果を、表1及び表2に示す。
表2に示すように、この電池はサイクル性能が高く、300サイクルまで劣化はなかった。
一酸化珪素((株)高純度化学研究所製、1μm)500gを用いて、複合化処理を行うことなく、実施例1と同様に化学蒸着処理を行った。この試料を用いて、実施例1と同様に電池性能の評価を行った。結果を、表1及び表2に示す。
表2に示すように、この電池はサイクル性能が低く、100サイクルまでに劣化した。
一酸化珪素((株)高純度化学研究所製、1μm)500gに、黒鉛(中国産、10μm)粉末500gを加え、アルゴン雰囲気下で、振動ミルで12時間複合化処理した後、篩い分けにより53μm以下の複合粒子を得た。この試料を用いて、実施例1と同様に電池性能の評価を行った。結果を、表1及び表2に示す。
表2に示すように、この電池はサイクル性能が低く、100サイクルまでに劣化した。
──────────────────────────────────
酸化物/配合炭素/被覆炭素 平均粒子径 比表面積
(質量%) (μm) (m2/g)
──────────────────────────────────
実施例1 45/ 45 /10 18 3.7
実施例2 26/ 64 /10 21 4.5
実施例3 45/ 45 /10 19 4.0
比較例1 90/ 0 /10 2 12.6
比較例2 50/ 50 / 0 18 18.5
──────────────────────────────────
────────────────────────────────────
充電量 効率(%) 初期容量に対する容量維持率(%)
(mAh/g) 1st 10th 50th 100th 300th
────────────────────────────────────
実施例1 980 69.5 99.6 99.7 97.8 91.8
実施例2 700 75.7 99.5 99.3 99.6 98.6
実施例3 500 84.3 97.8 99.2 98.6 96.7
比較例1 1600 62.9 91.6 31.5 劣化 −
比較例2 900 56.5 96.5 52.2 劣化 −
────────────────────────────────────
Claims (6)
- リチウム合金を形成可能な金属又は半金属の酸化物を含有する平均粒子径0.1〜1μmの粒子と炭素含有粒子とが機械的粉砕処理により密着してなる複合粒子を核として該複合粒子表面に炭素からなる被覆層を形成してなり、比表面積が1〜4.5m 2 /gであることを特徴とするリチウム二次電池用負極材料。
- 平均粒子径が1〜50μmである請求項1に記載のリチウム二次電池用負極材料。
- 前記酸化物が珪素又はゲルマニウムの酸化物である請求項1又は2に記載のリチウム二次電池用負極材料。
- 前記炭素含有粒子が黒鉛である請求項1乃至3の何れかに記載のリチウム二次電池用負極材料。
- 請求項1乃至4の何れかに記載のリチウム二次電池用負極材料を用いたリチウム二次電池。
- リチウム合金を形成可能な金属又は半金属の酸化物であって平均粒子径0.1〜1μmの粒子と炭素との混合物を機械的粉砕処理することにより、該酸化物を含有する粒子と炭素含有粒子とが密着した複合粒子を形成する粒子核製造工程と、前記製造した複合粒子の表面に炭素からなる被覆層を形成する被覆層形成工程とからなり、前記被覆層形成工程において、化学蒸着処理により被覆層を形成するリチウム二次電池用負極材料の製造方法。
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