JP6236197B2 - リチウム電池用正極及びリチウム電池 - Google Patents
リチウム電池用正極及びリチウム電池 Download PDFInfo
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- JP6236197B2 JP6236197B2 JP2012027456A JP2012027456A JP6236197B2 JP 6236197 B2 JP6236197 B2 JP 6236197B2 JP 2012027456 A JP2012027456 A JP 2012027456A JP 2012027456 A JP2012027456 A JP 2012027456A JP 6236197 B2 JP6236197 B2 JP 6236197B2
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- Prior art keywords
- positive electrode
- lithium
- lithium battery
- active material
- composite oxide
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 64
- -1 phosphoric acid compound Chemical class 0.000 claims description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 36
- 239000010450 olivine Substances 0.000 claims description 34
- 229910052609 olivine Inorganic materials 0.000 claims description 34
- 239000002131 composite material Substances 0.000 claims description 31
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims description 27
- 229910019142 PO4 Inorganic materials 0.000 claims description 26
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
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- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
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Description
LiMPO4 (化学式1)
吸蔵:LiFePO4−xLi+−xe−→xFePO4+(1−x)LiFePO4
放出:FePO4+xLi++xe−→xLiFePO4
LixNi1−yM’yO2−zXz (化学式2)
LixNi1−y’−y”Coy’Aly”O2 (化学式3)
LiFePO4は、固相法で製造され、FeC2O4・2H2O、NH4H2PO4とLi2CO3を化学量論比を合わせて混合及び粉砕した後、製造される活物質質量の5%のスクロースを添加し、700℃でN2を流しつつ、不活性雰囲気下で8時間焼成してLiFePO4を合成した。
NCA正極活物質としてのLiNi0.8Co0.15Al0.05O2を製造するために、Ni、Co、Alのニトレート水和物を、化学量論比(Ni:Co:Al=0.8:0.15:0.05)に合わせて均一溶液を作り、アンモニア水でpH=9に合わせて共沈させた後、洗浄して150℃で6時間乾燥させた。その後、Li2CO3をモル比に合わせて混合して粉砕した後、750℃で12時間焼成して、LiNi0.8Co0.15Al0.05O2を合成した。
NCM正極活物質としてのLiNi0.6Co0.2Mn0.2O2を製造するために、Ni、Co、Mnのニトレート水和物を、化学量論比(Ni:Co:Mn=0.6:0.2:0.2)に合わせて均一溶液を作り、アンモニア水でpH=10に合わせて共沈させた後、洗浄して150℃で6時間乾燥させた。その後、Li2CO3をモル比に合わせて混合して粉砕した後、870℃で20時間焼成して、LiNi0.6Co0.2Mn0.2O2を合成した。
<実施例1〜5及び比較例1〜6:LFP(LiFePO4)及びNCA(LiNi0.8Co0.15Al0.05O2)の混合>
製造例1及び2で製造した正極活物質LiFePO4(以下、「LFP」とする)及びLiNi0.8Co0.15Al0.05O2(以下、「NCA」とする)の粉末を一定割合で混合した後、圧力を加えてペレットを製造した。
製造例1及び3で製造した正極活物質LiFePO4(LFP)及びLiNi0.6Co0.2Mn0.2O2(以下、「NCM」とする)の粉末を一定割合で混合した後、圧力を加えてペレットを製造した。
正極活物質として、前記製造例1及び2で製造したLFP(LiFePO4)及びNCA(LiNi0.8Co0.15Al0.05O2)を、前記実施例1〜5及び比較例1〜6で使用した組成割合で混合して準備した後、準備された正極活物質と、バインダとしてのポリフッ化ビニリデン(PVdF)と、導電剤としてのカーボンとを96:2:2の質量比で混合した後、N−メチルピロリドンで分散させて正極スラリを製造した。前記正極スラリを、60μm厚にアルミニウム箔上にコーティングして薄い極板状にした後、135℃で3時間以上乾燥させた後、圧延(pressing)して正極を製造した。
前記実施例11〜15及び比較例12〜17のリチウム二次電池に使われた正極極板に対し、金属リチウムを対極(counter electrode)として同じ電解質を使用したコインセルをもって充放電実験をした。前記コインセルに対し、正極活物質1g当たり15mAの電流で、電圧が4.0V(vs.Li)に至るまで充電し、また同じ電流で、電圧が2.0V(vs.Li)に至るまで放電した。次に、同じ電流と電圧との区間で、充電及び放電を50回反復した。初期効率(initial coulombic efficiency)は、下記数式1で表示され、寿命容量維持率は、下記数式2で表示され、率別容量維持率は、下記数式3で表示される。
初期効率[%]
=[1stサイクルでの放電容量/1stサイクルでの充電容量]×100 (数式1)
寿命容量維持率[%]
=100回目サイクルでの放電容量/2回目サイクルでの放電容量 (数式2)
率別容量維持率[%]
=当該C−rate条件での放電容量/初期0.1C−rate条件での放電容量
(数式3)
前記実施例15、比較例12,13,15,16及び17の正極混合組成によって製造されたリチウム二次電池の貫通実験を下記のように実施し、その結果を下記表7に共に示した。
L0:変化なし、L1:液漏れ、L2:発煙、L3:発熱200℃以下、L4:発熱200℃以上、L5:爆発
23 正極
24 セパレータ
25 電池容器
26 封入部材
30 リチウム二次電池
Claims (11)
- オリビン構造のリン酸化合物70〜99質量%と、リチウムニッケル複合酸化物1〜30質量%と、で100%となる混合物であり、
前記オリビン構造のリン酸化合物は、LiFePO4であり、
前記リチウムニッケル複合酸化物は、下記化学式2で表示されるニッケル含有リチウム遷移金属酸化物を含む、リチウム電池用正極であり、
前記リチウムニッケル複合酸化物の平均粒径は、前記オリビン構造のリン酸化合物の平均粒径よりも小さいか、又は、前記オリビン構造のリン酸化合物の平均粒径よりも大きく、
前記リチウム電池用正極の合材密度は、2.1g/cc以上2.7g/cc以下である、リチウム電池用正極。
LixNi1−yM’yO2−zXz (化学式2)
ここで、前記化学式2で、M’はCo、Al、Mn、Mg、Cr、Fe、Ti、Zr、Mo及びそれらの合金から選択される少なくとも1つの金属であり、
Xは、O、F、S及びPから選択される元素であり、
0.9≦x≦1.1、0≦y≦0.5及び0≦z≦2である。 - 前記yは、0≦y≦0.2であることを特徴とする、請求項1に記載のリチウム電池用正極。
- 前記リチウムニッケル複合酸化物は、下記化学式3で表示される化合物を含むことを特徴とする、請求項1または2に記載のリチウム電池用正極。
LixNi1−y’−y”Coy’Aly”O2 (化学式3)
前記化学式3で、0.9≦x≦1.1、0<y’+y”≦0.2及び0<y”≦0.1である。 - 前記リチウムニッケル複合酸化物が、LiNi0.8Co0.15Al0.05O2、LiNi0.6Co0.2Mn0.2O2及びそれらの組み合わせから選択されることを特徴とする、請求項1〜3のいずれか1項に記載のリチウム電池用正極。
- 前記オリビン構造のリン酸化合物は、50〜2,000nmの平均粒径を有する一次粒子を含むことを特徴とする、請求項1〜4のいずれか1項に記載のリチウム電池用正極。
- 前記オリビン構造のリン酸化合物は、一次粒子の集合体を含む二次粒子を含み、前記二次粒子は、1〜30μmの平均粒径(D50)を有することを特徴とする、請求項1〜5のいずれか1項に記載のリチウム電池用正極。
- 前記オリビン構造のリン酸化合物の表面に、非晶質層をさらに含むことを特徴とする、請求項1〜6のいずれか1項に記載のリチウム電池用正極。
- 前記非晶質層は、カーボンまたは金属酸化物を含むことを特徴とする、請求項7に記載のリチウム電池用正極。
- 前記リチウムニッケル複合酸化物は、平均粒径(D50)が0.2〜20μmであることを特徴とする、請求項1〜8のいずれか1項に記載のリチウム電池用正極。
- 前記オリビン構造のリン酸化合物の含有量が80〜95質量%であり、
前記リチウムニッケル複合酸化物の含有量が5〜20質量%であることを特徴とする、請求項1〜9のいずれか1項に記載のリチウム電池用正極。 - 請求項1〜請求項10のうちのいずれか1項に記載のリチウム電池用正極と、
前記リチウム電池用正極と対向して配される負極と、
前記リチウム電池用正極と前記負極との間に配されるセパレータと、
を含む、リチウム電池。
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WO2022209815A1 (ja) | 2021-04-01 | 2022-10-06 | 株式会社Gsユアサ | 非水電解質蓄電素子用正極活物質、非水電解質蓄電素子用正極、非水電解質蓄電素子、蓄電ユニット及び蓄電装置 |
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KR101718054B1 (ko) | 2017-03-21 |
KR20120104484A (ko) | 2012-09-21 |
EP2498323A2 (en) | 2012-09-12 |
JP2012190786A (ja) | 2012-10-04 |
EP2498323B1 (en) | 2015-10-07 |
EP2498323A3 (en) | 2013-02-20 |
CN102683696A (zh) | 2012-09-19 |
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US20120231341A1 (en) | 2012-09-13 |
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