JP2014502245A - リチウムマンガン複合酸化物及びその製造方法 - Google Patents
リチウムマンガン複合酸化物及びその製造方法 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 30
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 150000002500 ions Chemical class 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001694 spray drying Methods 0.000 claims abstract description 9
- 238000010298 pulverizing process Methods 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims description 72
- 239000000126 substance Substances 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 239000011268 mixed slurry Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000001238 wet grinding Methods 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 4
- 239000003990 capacitor Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000007774 positive electrode material Substances 0.000 description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 8
- 238000000804 electron spin resonance spectroscopy Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 206010021143 Hypoxia Diseases 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010285 flame spraying 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
- 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 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000011802 pulverized particle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
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- C01G53/54—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [Mn2O4]-, e.g. Li(NixMn2-x)O4, Li(MyNixMn2-x-y)O4
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Abstract
【選択図】なし
Description
Li1+aMn2−xMxO4
(前記式で、aは0〜0.2であり、xは0〜0.4であり、MはAl、Mg、Zr、Cu、Ni、Sn、Sr、Zn、Si及びこれらの混合よりなる群から選択されるものである)。
A={Mn4+存在量/(Mn3+イオン存在量+Mn4+イオン存在量)}×100
本発明はまた、前記化学式1で表されるリチウムマンガン複合酸化物を含む電気化学素子を提供する。前記電気化学素子は、リチウム二次電池又はハイブリッドキャパシタが含まれる。
本発明は、下記化学式1で表され、Mnが3+、4+の酸化数を有し、下記関係式1で定義される表面のMn3+イオン存在量とMn4+イオン存在量との比A値が95〜100であることを特徴とするリチウムマンガン複合酸化物及びこの製造方法を提供する。
Li1+aMn2−xMxO4
前記式で、aは0〜0.2であり、xは0〜0.4であり、MはAl、Mg、Zr、Cu、Ni、Sn、Sr、Zn、Si及びこれらの混合からなる群より選択されるものである。
A={Mn4+の存在量/(Mn3+イオンの存在量+Mn4+イオンの存在量)}×100
本発明は、湿式粉砕及び噴霧乾燥法を適用し、熱処理段階で酸化雰囲気を調節することによって、前記のような化学式1及び関係式1の条件を満たすリチウムマンガン複合酸化物を製造するための方法を提供する。
Li1+aMn2−xMxO4
(前記式で、aは0〜0.2であり、xは0〜0.4であり、MはAl、Mg、Zr、Cu、Ni、Sn、Sr、Zn、Si及びこれらの混合からなる群より選択されるものである)。
A={Mn4+の存在量/(Mn3+イオンの存在量+Mn4+イオンの存在量)}×100
前記関係式1で、Mn3+イオンの存在量とMn4+イオンの存在量との比であるA値は95〜100の範囲で調節されることが好ましい。前記A値が95以下の場合、Mn3+イオンの相対的存在量が多くなり、これによる構造的劣化により寿命特性が劣化することになる。
リチウム源としてLi2Co3、マンガン源としてMnO2、異種金属MとしてAl(OH)3又はMg(OH)2を必要な化学量論比に準じて400g基準で計量した後、蒸留水に固体/液体の割合が4:6になるように入れた。攪拌器にて400rpmで10分間攪拌した後、湿式粉砕装置(Netzsch、Mincer:登録商標)にて3800rpmで40分間粉砕して、粉砕された粒子の粒径D50が0.3μm以下、粘度は500cp以下になるようにした。湿式粉砕装置には直径0.65mmのジルコニアビーズ(Zirconia bead)を用いた。
前記熱処理時、空気を1L/minの速度で注入したことを除いては、前記実施例1と同様に製造した。
前記熱処理時、空気を3L/minの速度で注入したことを除いては、前記実施例1と同様に製造した。
前記熱処理時、空気を5L/minの速度で注入したことを除いては、前記実施例1と同様に製造した。
現在リチウム二次電池正極活物質として市販されているLiMn2O4を用いた。
前記実施例1〜4で製造された正極活物質の酸素欠乏(Oxygen deficiency)を、ESRを通じて分析し、その結果を図1に表した。
X線光電子分光法(X−ray photoelectron spectroscopy)は、固状で存在する多様な元素の酸化状態を明らかにするのに有用な道具である。前記実施例1〜4で製造された正極活物質Li1+aMn2−O4と比較例1の現在用いられている製品とをXPS分析のMn2P3/2スペクトルの曲線当てはめ(Curve−fitting)技術を用いて表面のMn原子の酸化数を決定して、その結果を下記表1に表した。
前記実施例1〜4で製造された正極活物質、導電剤としてカーボンブラック(Denka Black)、バインダーとしてポリフッ化ビニリデン(PVDF)を94:3:3の割合で添加して均一に混合し、溶媒としてN−メチルピロリドン(NMP)12mlを添加して均一な状態の混合物を製造した。この混合物を20μm厚のアルミニウム箔に均一に塗布し、130℃で1時間乾燥した後、クロムがコーティングされたロールプレスを用いて1トンの圧力を与え圧着して、100℃の真空オーブンで12時間乾燥した。
前記実施例1〜4と比較例1の正極活物質で製造されたテストセルの電気化学的特性を評価するために、電気化学分析装置(TOSCAT3100、Toyo社製)を利用し、25℃で0.1Cの放電率を適用して、4.3V〜3Vの領域にてカットオフして充放電実験を行い、その結果を図3に表した。
Claims (8)
- 下記化学式1で表され、
[化学式1]
Li1+aMn2−xMxO4
(式で、aは0〜0.2であり、xは0〜0.4であり、MはAl、Mg、Zr、Cu、Ni、Sn、Sr、Zn、Si及びこれらの混合からなる群より選択されるもの)、Mnが3+、4+の酸化数を有し、
下記関係式1で定義される、
[関係式1]
A={Mn4+の存在量/(Mn3+イオンの存在量+Mn4+イオンの存在量)}×100
表面のMn3+イオンの存在量とMn4+イオンの存在量との比A値が95〜100であることを特徴とするリチウムマンガン複合酸化物。 - 請求項1に記載の前記リチウムマンガン複合酸化物を含む電気化学素子。
- 前記電気化学素子は、リチウム二次電池又はハイブリッドキャパシタであるものである請求項1に記載の前記リチウムマンガン複合酸化物を含む電気化学素子。
- (a)リチウム源、マンガン源及び金属源を投入する段階と、
(b)前記リチウム源、マンガン源及び金属源を湿式ミリングして混合スラリを製造する段階と、
(c)前記(b)段階の混合スラリを噴霧乾燥して前駆体粒子を生成する段階と、
(d)前記(c)段階の前駆体を熱処理する段階を含むことを特徴とし、下記化学式1で表され、
[化学式1]
Li1+aMn2−xMxO4
(式で、aは0〜0.2であり、xは0〜0.4であり、MはAl、Mg、Zr、Cu、Ni、Sn、Sr、Zn、Si及びこれらの混合からなる群より選択されるもの)、Mnが3+、4+の酸化数を有し、
下記関係式1で定義される、
[関係式1]
A={Mn4+の存在量/(Mn3+イオンの存在量+Mn4+イオンの存在量)}×100
表面のMn3+イオンの存在量とMn4+イオンの存在量との比A値が95〜100であることを特徴とする、リチウムマンガン複合酸化物の製造方法。 - 前記(b)段階の混合スラリは、粒子の直径が0.3μm以下、粘度は500cp以下であることを特徴とする化学式1で表される、請求項4に記載のリチウムマンガン複合酸化物の製造方法。
- 前記(b)段階の湿式粉砕は、3000rpm〜4000rpmの攪拌速度で、30分〜60分間攪拌することを特徴とする、請求項4に記載のリチウムマンガン複合酸化物の製造方法。
- 前記(c)段階の噴霧乾燥は、空圧式噴霧形態で1bar〜5barの圧力条件にて行うものである、請求項4に記載のリチウムマンガン複合酸化物の製造方法。
- 前記(d)段階の熱処理は、1℃/min〜5℃/minの昇温速度で、700℃〜1000℃の温度に昇温後、1時間〜10時間、1L/min〜10L/minの速度で空気を注入する条件下で行うものである、請求項4に記載のリチウムマンガン複合酸化物の製造方法。
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KR20170055823A (ko) * | 2015-11-12 | 2017-05-22 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 양극 활물질, 이를 포함하는 양극 및 리튬 이차 전지 |
JP2022504835A (ja) * | 2018-10-10 | 2022-01-13 | ノースボルト エービー | リチウム遷移金属複合酸化物およびその製造方法 |
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