JP2015099794A - 非水電解質電池および電池パック - Google Patents
非水電解質電池および電池パック Download PDFInfo
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- JP2015099794A JP2015099794A JP2015016708A JP2015016708A JP2015099794A JP 2015099794 A JP2015099794 A JP 2015099794A JP 2015016708 A JP2015016708 A JP 2015016708A JP 2015016708 A JP2015016708 A JP 2015016708A JP 2015099794 A JP2015099794 A JP 2015099794A
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- Prior art keywords
- lithium
- battery
- negative electrode
- composite oxide
- positive electrode
- Prior art date
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 76
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- 239000002131 composite material Substances 0.000 claims abstract description 80
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 claims abstract description 69
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- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 42
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- -1 lithium transition metal Chemical class 0.000 description 29
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- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical class [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
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Abstract
【課題】抵抗増加を抑えることが可能な非水電解質電池および電池パックを提供する。
【解決手段】実施形態によれば、正極3と、負極4と、非水電解質と、外装部材7とを備える非水電解質電池が提供される。外装部材7には、正極3、負極4及び非水電解質が収容される。負極4は、炭酸リチウム及び水酸化リチウムのうち少なくとも一方からなるリチウム化合物を含むリチウムチタン複合酸化物よりなる活物質を含む。
【選択図】図1
Description
また、実施形態によれば、正極と、負極と、非水電解質と、外装部材とを備える非水電解質電池が提供される。外装部材には、正極、負極及び非水電解質が収容される。負極は、炭酸リチウム及び水酸化リチウムのうち少なくとも一方からなるリチウム化合物を含むリチウムチタン複合酸化物よりなる活物質を含む。非水電解質電池をSOC50%に調整し、55℃の恒温槽中に72時間放置した時の放置前の電池厚さをA、放置後の電池厚さをBとした時の膨れ量{(B−A)/A×100[%]}が3%以下であり、かつ放置前の電池抵抗C、放置後の電池抵抗をDとした時の抵抗増加率(D/C)が1.1以下である。
実施形態によれば、実施形態に係る非水電解質電池を含む電池パックが提供される。
第一の実施形態によれば、リチウムチタン複合酸化物を含む活物質が提供される。リチウムチタン複合酸化物は、炭酸リチウム及び水酸化リチウムのうち少なくとも一方からなるリチウム化合物を含む。リチウム化合物のリチウム量が0.017質量%以上0.073質量%以下である。
ここで、Nはリチウムチタン複合酸化物のリチウム化合物含有量(質量%)、M1はリチウム化合物1モル当りのLi質量で、M2はリチウム化合物1モルの質量である。
第二の実施形態によれば、正極と、負極と、非水電解質とを備える非水電解質電池が提供される。負極は、第一の実施形態の活物質を含む。以下、正極、負極、非水電解質について説明する。
正極は、正極集電体と、正極集電体の片面若しくは両面に担持され、正極活物質、正極導電剤及び結着剤を含む正極活物質含有層とを有する。
負極は、負極集電体と、負極集電体の片面若しくは両面に担持され、負極活物質、負極導電剤および結着剤を含む負極活物質含有層とを有する。
非水電解質は、電解質を有機溶媒に溶解することにより調整される液状非水電解質、液状電解質と高分子材料を複合化したゲル状非水電解質等が挙げられる。
第三の実施形態によれば、第二の実施形態の非水電解質電池を含む電池パックが提供される。非水電解質電池の数は1個でも、複数でも良い。複数個の場合、電池が直列もしくは並列に接続され、組電池を構成していることが望ましい。
<正極の作製>
まず、正極活物質としてリチウムマンガン酸化物(LiMn2O4)粉末92質量%、導電剤として炭素材料5質量%、ポリフッ化ビニリデン(PVdF)3質量%をN−メチルピロリドン(NMP)に加えて混合してスラリーを調製した。このスラリーを厚さ15μmのアルミニウム箔からなる集電体の両面に塗布した後、乾燥し、プレスすることにより電極密度が2.8g/cm3の正極を作製した。
炭酸リチウムとアナターゼ型酸化チタンを混合して、800℃で10時間の焼成によりスピネル型チタン酸リチウム(Li4Ti5O12)を合成した。得られたスピネル型チタン酸リチウム(Li4Ti5O12)を直径3mmのジルコニア製ボールをメディアとし、エタノール中で3時間ボールミル粉砕した。粉砕した粉末を純水に浸し、得られたスラリー中に0.1L/分で二酸化炭素を流入させながら1時間攪拌した。雰囲気温度は0℃に保持した。二酸化炭素の導入量は、洗浄処理を施す前のチタン酸リチウム中の炭酸リチウム1モルに対して1モルに相当した。その後、ろ過によってチタン酸リチウムを抽出し、500℃で1時間の熱処理を施して、平均粒径が0.9μmのスピネル型チタン酸リチウム粒子を合成した。スピネル型チタン酸リチウム粒子のN2吸着によるBET法での比表面積は、10.8m2/gであった。
正極、厚さ20μmのポリエチレン製の多孔質フィルムからなるセパレータ、負極、セパレータの順番に積層した後、渦巻き状に捲回した。これを90℃で加熱プレスすることにより、幅が33mmで、厚さが3.0mmの偏平状電極群を作製した。得られた電極群を、厚さが0.1mmのラミネートフィルムからなるパックに収納し、80℃で24時間真空乾燥を施した。
エチレンカーボネート(EC)とジエチルカーボネート(DEC)が体積比率1:2で混合された混合溶媒に、電解質としてのLiPF6を1mol/L溶解することにより液状非水電解質を調製した。
洗浄処理の条件を下記表1に示すように変更する以外は、同様の手法で合成したチタン酸リチウムを用いる以外は、実施例1と同様な手法で非水電解質二次電池を作製した。
洗浄処理に変えて1.5質量%の酢酸水溶液による酸処理を施した後、120℃16時間の乾燥処理を施したチタン酸リチウムを用いる以外は、実施例1と同様の手法で非水電解質二次電池を作製した。
炭酸リチウムとアナターゼ型酸化チタンを混合して、1050℃で10時間の焼成によりラムスデライト型チタン酸リチウム(Li2Ti3O7)を合成した。得られたラムスデライト型チタン酸リチウムに、実施例4と同様な条件で洗浄処理、ろ過及び再焼成を施すことにより、平均粒径が0.9μmで、N2吸着によるBET法での比表面積が10.0m2/gのラムスデライト型チタン酸リチウム粒子を合成した。得られたラムスデライト型チタン酸リチウム粒子を負極活物質に用いること以外は、実施例1と同様の手法で非水電解質二次電池を作製した。
炭酸リチウムとアナターゼ型酸化チタンを混合して、1050℃で10時間の焼成によりラムスデライト型チタン酸リチウム(Li2Ti3O7)を合成した。得られたラムスデライト型チタン酸リチウムに、比較例1と同様な条件で洗浄処理、ろ過及び再焼成を施すことにより、平均粒径が0.9μmで、N2吸着によるBET法での比表面積が10.2m2/gのラムスデライト型チタン酸リチウム粒子を合成した。得られたラムスデライト型チタン酸リチウム粒子を負極活物質に用いること以外は、実施例1と同様の手法で非水電解質二次電池を作製した。
以下、本願の出願当初の特許請求の範囲に記載された発明を付記する。
[1] 炭酸リチウム及び水酸化リチウムのうち少なくとも一方からなるリチウム化合物を含み、前記リチウム化合物のリチウム量が0.017質量%以上0.073質量%以下であるリチウムチタン複合酸化物を含むことを特徴とする活物質。
[2] 前記リチウムチタン複合酸化物は、スピネル型構造であることを特徴とする[1]記載の活物質。
[3] 前記リチウムチタン複合酸化物は、Li4+xTi5O12(0≦x≦3)で表されることを特徴とする[1]乃至[2]のいずれかに記載の活物質。
[4] 前記リチウムチタン複合酸化物は、平均粒径が10nm以上10μm以下の粒子であることを特徴とする[1]乃至[3]のいずれかに記載の活物質。
[5] 前記リチウムチタン複合酸化物は、比表面積が3m2/g以上50m2/g以下であることを特徴とする[1]乃至[4]のいずれかに記載の活物質。
[6] 正極と、[1]乃至[5]のいずれかに記載の活物質を含む負極と、非水電解質とを備えることを特徴とする非水電解質電池。
[7] [6]記載の非水電解質電池を備えることを特徴とする電池パック。
[8] リチウム塩及び酸化チタンを含む原料を焼成することによりリチウムチタン複合酸化物を合成する工程と、二酸化炭素を含む水で前記リチウムチタン複合酸化物を洗浄する工程とを含むことを特徴とする活物質の製造方法。
[9] 前記洗浄工程が施された前記リチウムチタン複合酸化物に熱処理を施す工程を含むことを特徴とする[8]記載の活物質の製造方法。
Claims (8)
- 正極と、
炭酸リチウム及び水酸化リチウムのうち少なくとも一方からなるリチウム化合物を含むリチウムチタン複合酸化物よりなる活物質を含む負極と、
非水電解質と、
前記正極、前記負極及び前記非水電解質が収容される外装部材と
を備える非水電解質電池であり、
前記非水電解質電池をSOC50%に調整し、55℃の恒温槽中に72時間放置した時の放置前の電池厚さをA、放置後の電池厚さをBとした時の膨れ量{(B−A)/A×100[%]}が3%以下であり、かつ放置前の電池抵抗C、放置後の電池抵抗をDとした時の抵抗増加率(D/C)が1.1以下である、非水電解質電池。 - 前記外装部材がラミネートフィルム製である、請求項1に記載の非水電解質電池。
- 前記リチウム化合物のリチウム量が0.017質量%以上0.073質量%以下である、請求項1または2に記載の非水電解質電池。
- 前記リチウムチタン複合酸化物は、スピネル型構造である、請求項1〜3のいずれか1項に記載の非水電解質電池。
- 前記リチウムチタン複合酸化物は、Li4+xTi5O12(0≦x≦3)で表される、請求項1〜4のいずれか1項に記載の非水電解質電池。
- 前記リチウムチタン複合酸化物は、平均粒径が10nm以上10μm以下の粒子である、請求項1〜5のいずれか1項に記載の非水電解質電池。
- 前記リチウムチタン複合酸化物は、比表面積が3m2/g以上50m2/g以下である、請求項1〜6のいずれか1項に記載の非水電解質電池。
- 請求項1〜7のいずれか1項に記載の非水電解質電池を備える電池パック。
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US13/722,292 US20130189584A1 (en) | 2012-01-19 | 2012-12-20 | Active material, active material production method, nonaqueous electrolyte battery, and battery pack |
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JP2017168318A (ja) * | 2016-03-16 | 2017-09-21 | 株式会社東芝 | 非水電解質電池、電池パック及び車両 |
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CN106876691A (zh) | 2017-06-20 |
KR101582437B1 (ko) | 2016-01-04 |
CN103219505B (zh) | 2017-04-12 |
JP2013149486A (ja) | 2013-08-01 |
US20130189584A1 (en) | 2013-07-25 |
CN103219505A (zh) | 2013-07-24 |
US20210313556A1 (en) | 2021-10-07 |
KR101519699B1 (ko) | 2015-05-12 |
CN106876691B (zh) | 2019-10-01 |
JP5694208B2 (ja) | 2015-04-01 |
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