TWI515168B - Production method of lithium manganate particles and nonaqueous electrolyte battery - Google Patents

Production method of lithium manganate particles and nonaqueous electrolyte battery Download PDF

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Publication number
TWI515168B
TWI515168B TW098131396A TW98131396A TWI515168B TW I515168 B TWI515168 B TW I515168B TW 098131396 A TW098131396 A TW 098131396A TW 98131396 A TW98131396 A TW 98131396A TW I515168 B TWI515168 B TW I515168B
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Taiwan
Prior art keywords
lithium manganate
compound
lithium
manganese
particle powder
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TW098131396A
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English (en)
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TW201026607A (en
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Kazumichi Koga
Masayuki Uegami
Hiroaki Masuguni
Kazutoshi Matsumoto
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Toda Kogyo Corp
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    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1235—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]2-, e.g. Li2Mn2O4, Li2[MxMn2-x]O4
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Description

錳酸鋰粒子粉末之製造方法及非水電解質蓄電池
本發明提供一種在高輸出下高溫安定性優異之錳酸鋰粒子粉末之製造方法。
近年來，AV設備或電腦等電子設備之可攜帶化、無線化急速進展，因而高度要求小型、輕量之具有高能量密度之蓄電池作為該等之驅動用電源。在該等狀況下，具有充放電電壓高，充放電電容亦大之優點之鋰離子蓄電池備受矚目。
過去，作為於具有4V級電壓之高能量型鋰離子蓄電池中有用之正極活性物質一般已知為尖晶石型構造之LiMn2O4、岩鹽型構造之LiMnO2、LiCoO2、LiCo1-xNixO2、LiNiO2等，其中LiCoO2雖具有高電壓及高電容之優點，但由於鈷原料之供給量少而有包含製造成本高之問題及廢棄電池之環境安全上之問題。因此，於供給量多且低成本下使用環境適應性良好之錳作為原料所作成之尖晶石構造型錳酸鋰粒子粉末(基本組成：LiMn2O4，以下亦同)之硏究被普遍進行。
如週知者，錳酸鋰粒子粉末可以特定之比例混合錳化合物與鋰化合物，並在700~1000℃之溫度範圍內燒成獲得。
然而，使用錳酸鋰粒子粉末作為鋰離子蓄電池之正極活性物質時，儘管具有高電壓及高能量密度，但會有充放電循環特性變差之問題。其原因為由於隨著重覆之充放電，結晶構造中之鋰離子之脫離‧插入舉動使結晶晶格伸縮，因為結晶之體積變化造成晶格破壞，或使錳溶解於電解液。
關於使用錳酸鋰粒子粉末之鋰離子蓄電池，目前最為要求的是抑制因為重複充放電造成充放電電容劣化，尤其是提高在高溫、低溫下之充放電循環特性。
為了提高充放電循環特性，有必要使由錳酸鋰粒子粉末所構成之正極活性物質之充填性優異，具有適度大小，且進而抑制錳溶出。作為其手段已進行有控制錳酸鋰粒子之粒徑及粒度分佈之方法，控制燒成溫度獲得高結晶錳酸鋰粒子粉末之方法，添加異種元素強化結晶結合力之方法，表面處理或混入添加物以抑制錳溶出之方法等。
迄今為止，已知有於錳酸鋰粒子粉末中含有鋁作為異種元素之一(專利文獻1~6)。另外，已知有在燒成時添加氧化硼、硼酸、硼酸鋰、硼酸銨作為硼源，獲得燒結助劑之效果(專利文獻7~11)。
分別記載有使錳酸鋰粒子粉末中含有Ca化合物及/或Ni化合物與Al化合物(專利文獻1)，使錳酸鋰粒子粉末中含有Al且限定X射線繞射之各繞射面之峰位置(專利文獻2)，使錳酸鋰粒子粉末中含有Al等之異種元素並分為多階段進行燒成(專利文獻3)，使錳酸鋰粒子粉末中含有Al且比表面積為0.5~0.8m2/g、鈉含有量為1000ppm以下之錳酸鋰(專利文獻4)，使錳酸鋰粒子粉末中含有Al等之異種元素且(400)面之半寬值為0.22°以下之結晶粒子之平均直徑為2μm以下之錳酸鋰(專利文獻5)，使錳酸鋰粒子粉末中含有Al等之異種元素且晶格尺寸為600埃以上之晶格歪斜為0.1%以下之錳酸鋰(專利文獻6)，使鋰化合物及二氧化錳及硼化合物在溫度600℃~800℃加熱處理且以將硼納入晶格內加以解釋之化學式表示之錳酸鋰(專利文獻7)，添加氧化物之熔點為800℃以下之元素及氟化合物，以將該等元素納入晶格內加以解釋之化學式表示之錳酸鋰(專利文獻8)，含有比該公報更少量之硼之含硼的錳酸鋰粒子粉末(專利文獻9)，規定使用四硼酸鋰作為硼酸物種之含有四硼酸鋰之錳酸鋰粒子粉末(專利文獻10)。
[先前技術文獻]
[專利文獻1]特開2000-294237號公報
[專利文獻2]特開2001-146425號公報
[專利文獻3]特開2001-328814號公報
[專利文獻4]特開2002-33099號公報
[專利文獻5]特開2002-316823號公報
[專利文獻6]特開2006-252940號公報
[專利文獻7]特開平8-195200號公報
[專利文獻8]特開2001-48547號公報
[專利文獻9]特開2002-42812號公報
[專利文獻10]特開2005-112710號公報
改善輸出特性及高溫特性之作為非水電解質蓄電池用之正極活性物質之錳酸鋰目前極度被要求，但目前依然無法獲得充分滿足必要要求之材料及製造方法。
亦即，前述專利文獻1~10係分別敘述關於以異種元素取代為金屬元素錳之一部分而成之錳酸鋰，或少量添加硼化合物而成之錳酸鋰，但仍無法滿足電池之高溫儲存特性，因此在實用性上不足。
本發明者等對添加元素之形狀或燒成溫度進行各種檢討之結果，而完成本發明。
前述技術之課題可藉由以下說明之本發明達成。
亦即，本發明為一種錳酸鋰粒子粉末之製造方法，其係將鋰化合物、錳化合物及硼化合物混合後，在800℃~1050℃之溫度範圍內燒成獲得錳酸鋰粒子粉末之製造方法，其特徵為上述硼化合物之平均粒徑(D50)為錳化合物之平均粒徑(D50)之15倍以下(本發明1)。
又，本發明係如本發明1所述之錳酸鋰粒子粉末之製造方法，其中硼化合物之平均粒徑(D50)為1μm~100μm(本發明2)。
且，本發明係如本發明1或2所述之錳酸鋰粒子粉末之製造方法，其中錳化合物之平均粒徑(D50)為1μm~20μm(本發明3)。
又，本發明係如本發明1至3中任一項之錳酸鋰粒子粉末之製造方法，其中所得錳酸鋰粒子粉末為由粒徑1μm以上之一次粒子凝聚或燒結而形成之二次粒子所形成，以化學式：Li1+xMn2-x-yYlyO4+B(Yl=Ni、Co、Mg、Fe、Al、Cr、Ti中之至少一種，0.03≦x≦0.15，0≦y≦0.20)表示，錳酸鋰粒子之二次粒子之平均粒徑(D50)為1μm~20μm，且粒度分佈(D90-D10)為2~40μm(本發明4)。
另外，本發明為一種非水電解質蓄電池，其係使用本發明1至4中任一項之錳酸鋰粒子粉末之製造方法獲得之錳酸鋰粒子粉末作為正極活性物質或其一部分(本發明5)。
以本發明製造之錳酸鋰粒子粉末由於為於高輸出，特別是高溫安定性優異，因此適合作為非水電解質蓄電池用之正極活性物質。
亦即，以特定量之比例混合錳化合物、鋰化合物、依據需要之異種元素之化合物、及細微化之硼化合物，在特定溫度下燒成，可獲得具有優異特性之錳酸鋰粒子粉末。
以下更詳細說明本發明之構成。
首先，描述本發明之錳酸鋰粒子粉末之製造方法。
於本發明，於將鋰化合物、錳化合物及硼化合物混合後，在800℃~1050℃之溫度範圍內燒成獲得錳酸鋰粒子粉末之製造方法中，所添加之硼化合物之二次粒子之平均粒徑(D50)成為錳化合物之二次粒子之平均粒徑(D50)之15倍以下者。
硼化合物之二次粒子之平均粒徑(D50)相對於錳化合物之二次粒子之平均粒徑(D50)超過15倍時，由於發生錳酸鋰之微粉末，因此使電池特性降低。又，燒成時溶解之硼之偏析變大，使錳酸鋰之凝聚程度產生偏差，成為容易產生凝聚破壞之部分。較好為2倍以上14倍以下，更好為3倍以上13倍以下。
本發明中使用之硼化合物之二次粒子之平均粒徑(D50)較好為1~100μm，更好為1~70μm。
本發明中使用之錳化合物之二次粒子之平均粒徑(D50)較好為1.0~20μm，更好為2.0~19μm。
本發明中之錳化合物舉例為四氧化三錳(Mn3O4)、二氧化錳(MnO2)等。尤其以使用四氧化三錳較佳。
本發明中使用之硼化合物舉例為硼酸、四硼酸鋰、氧化硼、硼酸銨等。特別是以使用硼酸較佳。
本發明中之鋰化合物舉例為碳酸鋰、氫氧化鋰等。最好使用碳酸鋰。
再者，錳酸鋰粒子粉末中，依據需要存在有選自Ni、Co、Mg、Fe、Al、Cr、Ti之至少一種異種元素時，亦可使用使鋰化合物、錳化合物、異種金屬元素之化合物及硼化合物混合並燒成之方法；使錳化合物與異種金屬元素複合化(藉由乾式法或濕式法表面被覆異種金屬元素之化合物之方法，於錳化合物之表面上析出異種金屬元素之化合物之方法等)之後，同時混合鋰化合物及硼化合物並經燒成之方法之任一種方法。
錳化合物與鋰化合物之混合比例以莫耳比計較好為Li/Mn=0.525~0.62左右，未達0.525時，雖電容高但因Jahn-Teller效果引起偏斜發生，因此充放電循環特性降低。另外，超過0.62時，初期電容不足。更好為0.530~0.610。
硼化合物燒成時，促使作為燒結助劑之錳酸鋰粒子之結晶成長。硼化合物較好以硼化合物中之硼相對於錳成為0.1~2.5莫耳%之量添加。未達0.1莫耳%時，無法充分獲得燒結促進效果。超過2.5莫耳%時，由於燒結促進效果已經飽和，因此添加必要量以上之量並不需要。又，錳酸鋰粒子之凝聚‧燒結程度過強，且由於會產生微粉而不適當。更好為0.3~2.0莫耳%。
本發明中之燒成溫度較好為800℃以上。未達800℃時，無法獲得由硼造成之粒子充分燒結促進效果。更好為850~1050℃。
燒成氛圍較好為含氧氣體，例如在空氣中即可。燒成時間只要選擇使反應均勻進行即可，但較好為1~48小時，更好為10~24小時。
再者，硼化合物在燒成時，錳酸鋰粒子之邊緣(有稜角之部分：結晶面與結晶面結合之部位)變鈍，成為帶有圓邊之粒子之效果。過去於錳酸鋰自其粒子邊緣部份發生錳之溶出被認為是電池特性，尤其是高溫時之特性惡化之原因。本發明中認為，錳酸鋰粒子之邊緣(稜角部分)變鈍，成為帶有圓邊之粒子，可減少錳之溶出部位，結果可提高蓄電池之安定性。
另外，硼化合物燒成時，被認為會與鋰化合物中之鋰反應形成B-Li系化合物。該B-Li系化合物由於被認為在800℃以上融解，因而被認為以被覆錳酸鋰粒子之狀態存在。另外，由於以粉末X射線繞射計(XRD)測定該錳酸鋰粒子亦無法檢出含硼之結晶相，因而B-Li系化合物被認為以非結晶質狀態存在。該B-Li系化合物係扮演一種保護膜之角色，尤其是被認為可防止高溫時錳溶出。
硼化合物之平均粒徑大於本發明之範圍時，認為燒成時過量產生之B-Li系化合物會與氧強力結合。該B-Li系化合物膜過厚時(硼之添加量過量時)，被認為會妨礙燒成時應納入之氧朝錳酸鋰晶格內之擴散。因此，認為晶格內無法完全納入必要之氧，使錳酸鋰粒子粉末成為氧缺損之狀態，因而被認為容易使尖晶石構造歪斜。歪斜之晶格由於為錳之束縛原因之氧減少，因而容易成為錳容易溶出之狀態。
本發明中，認為硼化合物依據本發明使粒徑較小可偏在於錳酸鋰粒子之粒子表面，且B-Li系化合物膜較薄，可獲得氧缺損較少、錳的溶出獲得抑制之錳酸鋰粒子。又，本發明中，更好硼化合物在錳酸鋰粒子之粒子表面上均一分佈。
接著，對以本發明之錳酸鋰粒子粉末之製造方法獲得之錳酸鋰粒子粉末加以描述。
本發明中，錳酸鋰粒子粉末之化學式為Li1+xMn2-x-yYlyO4+B，Yl較好為選自Ni、Co、Mg、Fe、Al、Cr、Ti之至少一種。
其中，x較好為0.03~0.15，y較好為0~0.20。
x未達0.03時，電容雖變高但高溫特性顯著降低。超過0.15時，高溫特性獲得改善，但電容顯著降低，成為生成Li溶出相使阻抗上升之原因。更好為0.05~0.15。
y超過0.20時由於電容大降低而不置用。較好為0.01~0.20，更好為0.05~0.15。
認為硼形成B-Li系化合物並被覆錳酸鋰粒子。認為硼不含在錳酸鋰粒子之晶格內，B-Li系化合物存在於粒子表面附近，且以非晶質狀態存在。該B-Li系化合物被認為係扮演一種保護膜之角色，尤其在高溫下可防止錳之溶出。硼元素亦存在於錳酸鋰之粒子內部時，製備蓄電池時會使安定性下降。
硼含量相對於錳為0.1~2.5莫耳%。硼含量相對於錳未達0.1莫耳%時，B-Li系化合物無法充分被覆錳酸鋰粒子，無法獲得抑制錳溶出之效果。超過2.5莫耳%時，由於發生錳酸鋰之微粉，故電池特性下降。硼之含量相對於錳更好為0.3~2.0莫耳%。
本發明中之錳酸鋰粒子粉末之二次粒子之平均粒徑(D50)較好為1~20μm。平均粒徑未達1μm時，安定性下降。平均粒徑超過20μm時，輸出下降。更好為2~15μm，又更好為3~10μm。
又，本發明中之錳酸鋰粒子粉末之二次粒子之粒度分佈寬度(D90-D10)較好為2~30μm。超過前述粒度分佈之寬度(D90-D10)時，粒度分佈廣而不佳。更好粒度分佈之寬度為3~20μm。
本發明中添加之硼化合物之尺寸較大時，燒成時錳化合物無法均勻附著，造成錳酸鋰之二次粒子彼此之結合局部增加。又，由於會發生微粉，因此(D90-D10)之寬度不宜大。
依據本發明之製作，可抑制微粉發生，抑制二次粒子彼此之結合，結果，可使(D90-D10)之寬度變小。
又，構成本發明中之錳酸鋰粒子粉末之一次粒子之平均粒徑為1μm以上。一次粒徑未達1μm時，安定性下降。超過15μm時，會使蓄電池之輸出下降。更好為1.2~13.0μm。
接著，就使用由本發明中之非水電解質二次電池用錳酸鋰粒子粉末所構成之正極活性物質而成之正極加以描述。
使用本發明中之正極活性物質製造正極時，係依據慣用方法添加混合導電劑與黏著劑。導電劑較好為乙炔黑、碳黑、石墨等，黏著劑較好為聚四氟乙烯、聚偏氟乙烯等。
使用本發明之正極活性物質製造之蓄電池係由上述正極、負極及電解質構成。
負極活性物質可使用鋰金屬、鋰/鋁合金、鋰/錫合金、石墨或黑鉛等。
另外，作為電解液之溶劑，除碳酸乙烯酯與碳酸二乙酯之組合以外，亦可使用包含碳酸丙烯酯、碳酸二甲酯等碳酸酯類，或二甲氧基乙烷等醚類之至少一種之有機溶劑。
再者，電解質除六氟化磷酸鋰以外，可使用將過氧化鋰、四氟化硼酸鋰等鋰鹽之至少一種類溶解於上述溶劑中而成者。
<作用>
本發明之重點為使硼化合物之平均粒徑(D50)成為錳化合物之平均粒徑(D50)之15倍以下。
本發明中，藉由使硼化合物之平均粒徑(D50)成為錳化合物之平均粒徑(D50)之15倍以下，對錳化合物粒子整體可均勻的執行燒結助劑效果，且燒成過程中生成之B-Li系化合物薄薄地被覆在錳酸鋰粒子上，因此即使添加少量的硼化合物，亦可強固地促進粒子彼此之燒結。
又，大量添加硼化合物時，燒成後粉碎時有產生大量微粉之情況。然而，依據本發明藉由使硼化合物之粒徑較小，即使少量添加硼化合物亦可獲得充分之燒結促進效果，因此可抑制粉碎時微粉之發生。
又，使硼化合物之平均粒徑(D50)成為錳化合物之平均粒徑(D50)之15倍以下，容易均勻地混合鋰化合物與錳化合物及硼化合物，且錳酸鋰粒子粉末燒成時，可薄且均勻地製備B-Li系化合物之被膜，藉由使該被膜較薄而容易吸收氧，結果可製作不易引起氧缺損之錳酸鋰粒子。
[實施例]
以下說明本發明代表之實施形態。
關於錳化合物及猛酸鋰之平均粒徑(D50)為使用雷射式粒度分佈測定裝置MICROTRACK HRA[日機裝(股)製造]，以濕式雷射法測定之體積基準之平均粒徑。關於硼化合物係使用HELOS粒度分佈測定裝置(Sympatec公司製造)，以乾式雷射法測定之體積基準之平均粒徑。
平均粒徑(D50)為相對於以錳酸鋰粒子粉末之全部體積作為100%之粒徑求得累積比例時之累積比例成為50%之粒徑。又，相對於以錳酸鋰粒子粉末之全部體積作為100%之粒徑求得累積比例時之累積比例成為10%之粒徑作為D10，以錳酸鋰粒子粉末之全部體積成為100%求得以累積體積表示之粒徑時之累積比例成為90%之粒徑作為D90。
粒度分佈之寬度(D90-D10)為自上述D90減掉D10之值。
錳酸鋰粒子粉末之一次粒子之平均粒徑係自SEM照片讀取平均值。
藉由使用錳酸鋰粒子粉末之硬幣型電池進行初期充放電特性及高溫保存特性之評價。
首先，使92重量%之作為正極活性物質之錳酸鋰粒子粉末、2.5重量%之作為導電材之乙炔黑及2.5重量%之石墨KS-15、3重量%之作為結合劑之溶解於N-甲基吡咯啶酮中之聚偏氟乙烯予以混合後，塗佈於Al金屬箔上且於120℃下乾燥。將該薄片沖打出直徑16mm後，在1.5t/cm2下壓著，於正極使用電極厚度成為50μm之物。負極為沖壓出直徑16mm之金屬鋰，電解液係使用溶解1mol/L之LiPF6而成之以體積比3：7混合EC與DEC之溶液，製作CR2032型硬幣電池。
初期充放電特性係在室溫下以0.1C之電流密度進行充電至4.3V，進行90分鐘之定電壓充電後，以0.1C之電流密度進行放電至3.0V，測定此時之初期充電電容、初期放電電容及初期效率。
又，進行高溫循環試驗作為高溫時之特性。試驗係在60℃之恆溫槽中，在電壓範圍成為3.0~4.3下，在0.1C之C速率下進行1次循環、11次循環、21次循環、31次循環之充放電，其他循環係在1C之速率下重複充放電。關於「高溫循環電容維持率」為相對於初次放電電容之第31次放電電容之比例。又，「速率特性」為第30次循環與第31次循環之比例(第30次循環/第31循環×100)。
關於氧缺損，可以0.1C放電時達到3.3V~3.0V之比電容(3.3V Foot)之測定加以判斷。發生氧缺損時，放電時在3.3V~3.0V之領域中發生停滯區域，其比電容尤其在成為1.0mAh/g以上時，氧缺損狀態變大，為錳容易大量溶出之狀態。
實施例1：
在通氮氣之下，於3.5莫耳之氫氧化鈉中添加0.5莫耳之硫酸錳，使總量成為1升，使所得氫氧化錳在90℃下熟成1小時。熟成後，通入空氣且在90℃下氧化，經水洗、乾燥後獲得氧化錳粒子粉末。
所得氧化錳粒子粉末為Mn3O4，粒子形狀為粒狀，平均粒徑為4.8μm。
含有上述氧化錳粒子之水性懸浮液使用過濾器壓製機，以5倍量之水進行水洗後，使氧化錳粒子之濃度成為10wt%之方式交會。對於懸浮液以使Mn：Al=95：5之方式，將0.2mol/L之鋁酸鈉水溶液連續供給於反應槽內。反應槽係以攪拌機經常進行攪拌，同時以成為pH=8±0.5之方式自動進行0.2mol/L之硫酸水溶液之供給，獲得包含以氫氧化鋁被覆之氧化錳粒子之懸浮液。
該懸浮液使用過濾器壓製機，以相對於該氧化錳粒子之重量10倍之水進行水洗後，進行乾燥，獲得Mn：Al=95：5之平均二次粒徑4.8μm之以氫氧化鋁被覆之氧化錳粒子。
使所得之以氫氧化鋁被覆之Mn3O4粒子粉末與碳酸鋰及平均二次粒徑18.2μm之硼酸以Li：Mn：Al=1.072：1.828：0.10，硼酸中之硼相對於錳為1.5mol%之比例秤量硼酸，經乾式混合1小時，獲得均勻混合物。將30克所得混合物倒入氧化鋁坩堝中，在910℃、空氣氛圍中保持3小時，獲得錳酸鋰粒子粉末。所得錳酸鋰粒子粉末之X射線繞射並未檢出有關於添加之硼及硼化合物之峰，確認為錳酸鋰單相。所得錳酸鋰粒子粉末之SEM相片顯示於圖1中，使用之硼酸之SEM相片顯示於圖2中。如圖1中所示，所得錳酸鋰粒子粉末沒有粒子稜角部份，確認為帶有圓邊之粒子。
所得錳酸鋰粒子粉末組成設為Li1+xMn2-x-yYlyO4時，x為0.072，y為0.10，平均一次粒徑為4μm，二次粒子之平均粒徑(D50)為8.8μm。
又，將5克之錳酸鋰粉末、100毫升純水投入200毫升之燒杯中，煮沸7分鐘，經冷卻後，以No. 5B濾紙過濾成為溶液使用，以ICP鑑定元素，進行可溶性試驗之結果。結果，硼完全溶解。據此，確認硼僅存在於錳酸鋰粒子粉末之表面上。又，由於與硼溶解之量成比例溶解Li，因此推定硼與Li化合物化。
使用由此處獲得之錳酸鋰粒子粉末所構成之正極活性物質製作之硬幣型電池之初期放電電容為108mAh/g，氧缺損相關之比電容(3.3V Foot)為0.223mAh/g。又，在60℃下31次循環後之電容維持率為97%，速率特性為99.6%。
實施例2~3及5：
除使用之硼化合物之粒徑、燒成溫度經種種變化以外，餘如上述實施例1般獲得錳酸鋰粒子粉末。此時之製造條件列於表1中，所得錳酸鋰粒子粉末之諸特性列於表2中。
實施例4：
除不使用被覆氧化錳化合物粒子之Yl元素以外，餘如上述實施例1般獲得錳酸鋰粒子粉末。此時之製造條件列於表1中，所得錳酸鋰粒子粉末之諸特性列於表2中。
比較例1：
除使用以氫氧化鋁被覆之平均二次粒徑為4.8μm之Mn3O4粒子粉末與平均粒徑(D50)為193μm之硼酸以外，餘如上述實施例1般，獲得錳酸鋰粒子粉末。所得錳酸鋰粒子粉末之SEM相片示於圖3，使用之硼酸之SEM相片示於圖4。又，此時之製造條件列於表1中，所得錳酸鋰粒子粉末之諸特性列於表2中。
比較例2：
除使用之錳化合物及硼化合物之平均粒徑經種種變化以外，餘如上述實施例1般獲得錳酸鋰粒子粉末。此時之製造條件列於表1中，所得錳酸鋰粒子粉末之諸特性列於表2中。
比較例3：
除使用之錳化合物及硼化合物之粒徑、Li之混合量經各種變化，且未使用被覆氧化錳化合物粒子之Yl元素以外，餘如上述比較例2般獲得錳酸鋰粒子粉末。此時之製造條件列於表1中。所得錳酸鋰粒子粉末之諸特性列於表2中。
由以上之結果，相較於實施例1，比較例1中獲得之錳酸鋰粒子粉末發生多量微粉。另外，比較例中獲得之錳酸鋰粒子粉末有關於氧缺損之比電容高，認為是因氧缺損所造成。結果，無法抑制錳之溶出，電池之高溫循環特性下降的同時，亦認為為速率特性變差者。
[產業上利用之可能性]
本發明之錳酸鋰粒子粉末之製造方法由於可獲得結晶性高、輸出特性高、高溫儲存特性優異之可較好地作為蓄電池用正極活性物質之錳酸鋰，因此作為錳酸鋰粒子粉末之製造方法為較佳。
圖1為實施例1中獲得之錳酸鋰粒子粉末之SEM相片(倍率5000倍)。
圖2為實施例1中使用之H3BO3之SEM相片(倍率100倍)。
圖3為比較例1中獲得之錳酸鋰粒子粉末之SEM相片(倍率5000倍)。
圖4為比較例1中使用之H3BO3之SEM相片(倍率50倍)。

Claims (4)

  1. 一種錳酸鋰粒子粉末之製造方法，其係將鋰化合物、錳化合物及硼化合物混合後，在800℃~1050℃之溫度範圍內燒成獲得錳酸鋰粒子粉末之製造方法，其特徵為上述硼化合物之平均粒徑(D50)為錳化合物之平均粒徑(D50)之15倍以下，錳化合物與鋰化合物之混合比例以莫耳比計為Li/Mn=0.525~0.62，硼化合物之混合比例相對於Mn而言，硼為0.1~2.5莫耳%，且硼化合物之平均粒徑(D50)為1μm~100μm。
  2. 如申請專利範圍第1項之錳酸鋰粒子粉末之製造方法，其中錳化合物之平均粒徑(D50)為1μm~20μm。
  3. 如申請專利範圍第1或2項之錳酸鋰粒子粉末之製造方法，其中所得錳酸鋰粒子粉末為由粒徑1μm以上之一次粒子凝聚或燒結而形成之二次粒子所形成，以化學式：Li1+xMn2-x-yY1yO4+B(Y1=Ni、Co、Mg、Fe、Al、Cr、Ti中之至少一種，0.03≦x≦0.15，0≦y≦0.20)表示，錳酸鋰粒子之二次粒子之平均粒徑(D50)為1μm~20μm，且粒度分佈之寬度(D90-D10)為2~30μm。
  4. 一種非水電解質蓄電池，其係使用申請專利範圍第1至3項中任一項之錳酸鋰粒子粉末之製造方法獲得之錳酸鋰粒子粉末作為正極活性物質或其一部分。
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CN102149641B (zh) 2014-12-10
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JP5472602B2 (ja) 2014-04-16
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