JP2004083388A - Lithium manganese composite oxide granule secondary particle and method for producing the same and application thereof - Google Patents
Lithium manganese composite oxide granule secondary particle and method for producing the same and application thereof Download PDFInfo
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- JP2004083388A JP2004083388A JP2003043243A JP2003043243A JP2004083388A JP 2004083388 A JP2004083388 A JP 2004083388A JP 2003043243 A JP2003043243 A JP 2003043243A JP 2003043243 A JP2003043243 A JP 2003043243A JP 2004083388 A JP2004083388 A JP 2004083388A
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000011163 secondary particle Substances 0.000 title claims abstract description 40
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000008187 granular material Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 48
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 8
- 239000011164 primary particle Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 53
- 239000011572 manganese Substances 0.000 claims description 43
- 239000002245 particle Substances 0.000 claims description 38
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 32
- 239000004327 boric acid Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 21
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 20
- -1 boric acid compound Chemical class 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007774 positive electrode material Substances 0.000 claims description 16
- 238000001694 spray drying Methods 0.000 claims description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 150000001639 boron compounds Chemical class 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 239000012535 impurity Substances 0.000 claims 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- WIULKJSHHWSNQM-UHFFFAOYSA-N lithium sodium hydrogen borate Chemical compound B([O-])([O-])O.[Na+].[Li+] WIULKJSHHWSNQM-UHFFFAOYSA-N 0.000 claims 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical group [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 239000013543 active substance Substances 0.000 abstract 1
- 230000004931 aggregating effect Effects 0.000 abstract 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical group CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 6
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 6
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 239000004677 Nylon 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
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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- 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
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- Inorganic Compounds Of Heavy Metals (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
リチウムマンガン複合酸化物粉末及びその製造方法並びにその用途である非水電解質二次電池に関する。
【０００２】
【従来の技術】
リチウムマンガン複合酸化物を非水電解質二次電池の正極活物質として使用する際、結晶一次粒子が燒結した適当な大きさの顆粒二次粒子からなる粉末が用いられている。顆粒二次粒子の製造方法としては、従来からいくつかの方法が適用されてきた。例えば、特開２０００−１６９１５１号公報には電解二酸化マンガンと炭酸リチウムの反応からリチウムマンガン複合酸化物を得る際、出発物質である電解二酸化マンガンの大きさを粉砕調整することにより、反応後もその大きさを保った顆粒二次粒子とする方法が、特開平１０−１７２５６７号公報には、電解二酸化マンガン粉末を水溶性リチウム化合物の水溶液に分散させたスラリーを噴霧乾燥し、造粒して顆粒二次粒子とする方法が、また、特開平１０−２２８５１５号公報及び特開平１０−２９７９２４号公報には微粉末をローラコンパクター等を用い圧密・塊成化して顆粒二次粒子とする方法が開示されている。
【０００３】
これらの開示資料からも知られるように、従来は電池の体積当たりの放電容量を高める観点から、顆粒二次粒子をできるだけ緻密にし、粉末の充填密度を高くすることに重点がおかれてきた。従って、これまで顆粒二次粒子の組織、特に内在する気孔について特徴付けた例は少ない。
【０００４】
顆粒二次粒子に内在する気孔について特徴付けたものとしては、例えば、特開２００２−７５３６５号公報がある。これは正極活物質の粒子内部に空孔を形成させることによりハイレート充放電特性およびサイクル特性に優れる正極活物質を提供しようとするものである。しかしこの空孔は閉孔であり、空孔が粒子外部環境と通じていないので、電解液へのリチウムイオンの拡散が十分におこなわれておらず、ハイレート特性およびサイクル特性の改善が不十分なものであった。即ち、上記公報第５頁の表２に、ハイレート充放電特性として２．０クーロン通電した時の容量と０．２クーロン通電した時の容量の比で評価しているが、その容量比は９０％以下となり、ハイレート充放電特性としては不十分である。
【０００５】
【発明が解決しようとする課題】
本発明はリチウムマンガン複合酸化物の顆粒二次粒子の組織制御を課題とし、特に顆粒内の開気孔形態に着目してなされた。高出力特性を示す非水電解質二次電池の構成材料として適するリチウムマンガン複合酸化物正極活物質、並びにその製造方法を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明はリチウムマンガン複合酸化物の顆粒二次粒子に存在する開気孔の大きさと量が、この酸化物を正極活物質とする非水電解質二次電池の放電レート特性（特開２００２−７５３６５号公報でのハイレート充放電特性と対応する特性）を支配する因子であることを見出すことによって成し遂げられた。すなわち、本発明のリチウムマンガン複合酸化物顆粒二次粒子は、粒子内にマイクロメーターサイズの開気孔が網目状に多数存在し、その孔の大きさが平均径として０．５〜３μｍの範囲にあり、且つその量が顆粒体積に対して平均３〜２０ｖｏｌ．％の範囲にあることを特徴とする。
【０００７】
最大の特徴は、顆粒二次粒子（以下、単に「顆粒」と略称することもある）内にマイクロメーターサイズの開気孔を網目状に多数存在させることにある。この結果として、電池の放電レート特性の向上が図れる。
【０００８】
マイクロメーターサイズの開気孔は大きさと量で規定され、大きさは平均径として０．５〜３μｍ、量は顆粒体積に対して平均３〜２０ｖｏｌ．％である。気孔の平均径が０．５μｍ未満では電池の放電レート特性が低下する。また、３μｍを超える開気孔になると顆粒の強度を保つことが困難となる。最も好ましい平均径は１．０〜２．５μｍの範囲である。
【０００９】
開気孔の割合は、３ｖｏｌ．％未満では電池の放電レート特性が低下し、また２０ｖｏｌ．％を超えると電極材料として要求される高い粉末充填密度を確保することが困難となる。最も好ましい開気孔の割合は５〜１５ｖｏｌ．％である。
【００１０】
なお、開気孔の平均径及び量は開気孔を球形近似して求められる値であり、測定方法として顆粒の切断面の走査型電子顕微鏡写真を撮り、画像解析処理する方法によって知ることができ、ここでは気孔数５００個以上の平均から求めた個数平均値とする。
【００１１】
本発明の顆粒二次粒子は開気孔を多数有する以外に、比表面積０．２〜１．０ｍ２／ｇ、顆粒二次粒子の平均径５〜３０μｍ、顆粒を構成する結晶一次粒子の平均径が０．５〜４．０μｍであることにより特徴付けられる。これらの値は正極活物質として二次電池性能を最大限引き出すために特定される。例えば比表面積１．０ｍ２／ｇを超えたり、或いは結晶一次粒子径０．５μｍ未満では、５０℃以上の温度において、充放電容量のサイクル劣化が顕著となるので好ましくなく、比表面積０．２ｍ２／ｇ未満、或いは結晶一次粒子径４．０μｍを超えると放電レート特性の低下をきたすので好ましくない。顆粒二次粒子の平均径は５〜３０μｍの範囲外になると、シート電極を構成する上で不都合となり適切でない。
【００１２】
本発明のリチウムマンガン複合酸化物は、好ましくは、組成式ＬｉＸＭＹＭｎ３−Ｘ−ＹＯ４−ＺＦＺ（式中、Ｘ＝１．０〜１．２、Ｙ＝０〜０．３、Ｚ＝０〜０．３、Ｍ：Ａｌ，Ｃｏ，Ｎｉ，Ｃｒ，Ｆｅ及びＭｇから選ばれる１種以上の元素）で表示される。充放電容量と充放電繰り返し安定性を決定する上でＬｉ含量Ｘと添加元素Ｍの含量Ｙは重要で、特に好ましい範囲としては、Ｘ＝１．０５〜１．１５、Ｙ＝０．０５〜０．２５、Ｘ＋Ｙ＝１．１５〜１．３０が選ばれる。
【００１３】
ホウ酸化合物が一定量以上顆粒表面及び開気孔内部に存在すると電池性能に悪影響を及ぼす。ホウ酸化合物が電池性能に影響しない好ましい範囲はマンガンに対するモル比で０＜Ｂ／Ｍｎ＜０．０００５であり、０＜Ｂ／Ｍｎ＜０．０００３であることがさらに好ましい。
【００１４】
本発明の粉末の製造方法はマンガン酸化物の微粉末と炭酸リチウムの微粉末を分散したスラリーを噴霧乾燥により顆粒化した後、７００〜９００℃の温度で焼成すること、又はマンガン酸化物の微粉末とリチウム原料および開気孔形成剤を分散したスラリーを、噴霧乾燥により顆粒化した後、７００〜９００℃の温度で焼成することを特徴とする。
【００１５】
マンガン酸化物の粉末としては、電解二酸化マンガン、化学合成二酸化マンガン、Ｍｎ３Ｏ４、Ｍｎ２Ｏ３等が挙げられる。
【００１６】
リチウム源としては、水溶性の水酸化リチウム、或いは硝酸リチウム等と、水に不溶性の炭酸リチウムが挙げられる。水に不溶性の炭酸リチウムをリチウム源として用いる場合は、この炭酸リチウムが開気孔形成剤としても働く為、炭酸リチウム及びマンガン酸化物の粒子サイズが気孔の大きさを支配する因子として重要となる。その粒子サイズはサブミクロンオーダーが適当であり、炭酸リチウムとマンガン酸化物混合粉末の平均粒子径として１μｍ以下が好ましく、０．３〜０．７μｍの範囲がさらに好ましい。このような粒子サイズはマンガン酸化物の粉末と炭酸リチウムの粉末を水に入れ、粉砕混合することで容易に達成される。粉砕混合装置としては、ボールミル、振動ミル、湿式媒体攪拌式ミル等が使用できる。
【００１７】
尚、開気孔の全体積を大きくしたい場合には、炭酸リチウム以外の開気孔系製剤を添加してもよい。
【００１８】
リチウム源として、炭酸リチウムの他に水溶性の水酸化リチウム、或いは硝酸リチウム等をリチウム源として使用できる。
【００１９】
この場合、開気孔形成剤を使用しなければならず、その粒子サイズが気孔の大きさを支配する因子として重要となる。その粒子サイズはサブミクロンオーダーが適当であり、具体的には１μｍ以下が好ましく、０．３〜０．７μｍの範囲がさらに好ましい。このような粒子サイズはマンガン酸化物の粉末とリチウム原料および開気孔形成剤粉末を水に入れ、粉砕混合することで容易に達成される。粉砕混合装置としては、ボールミル、振動ミル、湿式媒体攪拌式ミル等が使用できる。
【００２０】
開気孔形成剤としては、カーボンブラック，カーボンナノチューブ，グラファイト等に例示されるような、加熱により消失する物質を用いる。
【００２１】
開気孔形成剤の量および炭酸リチウムの量により気孔量が制御できる。気孔量は顆粒体積に対して平均３〜２０ｖｏｌ．％が好ましく、５〜１５ｖｏｌ．％が最も好ましい。
【００２２】
湿式粉砕混合されたスラリーは噴霧乾燥により顆粒化される。噴霧乾燥はスラリーを回転ディスク、或いは流体ノズルで噴霧し、液滴を熱風で乾燥する通常のスプレードライヤーで行うことができる。顆粒化の方法として、噴霧乾燥以外の方法例えば液中造粒法、転動造粒法等が適用できるが、噴霧乾燥が最も工業的に有利である。
【００２３】
本願発明のリチウムマンガン複合酸化物の二次正極材料としての性能を高める目的で、マンガン、リチウム以外の元素の化合物、例えばアルミニウム、クロム等の化合物を添加元素として加えることがしばしば行われているが、添加元素Ｍを加える場合はその元素の酸化物、またはその前駆物質（水酸化物等）の形で加えるのがよく、その添加方法は粉砕混合の前にマンガン酸化物と炭酸リチウムからなるスラリーに添加することが適切である。
【００２４】
請求項１１に記載のホウ素化合物の添加はリチウムマンガン複合酸化物の結晶一次粒子の形状を制御する目的により行われる。これにより、開気孔の均一な網目状化が達成される。ホウ素化合物としては、Ｈ３ＢＯ３、Ｂ２Ｏ３及びＬｉ２Ｏ・ｎＢ２Ｏ３（ｎ＝１〜５）等を用いることができ、添加は焼成前でなければならず、噴霧乾燥前のスラリーに入れるのが適当である。添加量は、マンガンに対するモル比で０．０００５〜０．０５の範囲であり、０．０１〜０．００１の範囲が更に好ましい。ホウ素化合物は焼成後、ホウ酸化合物として複合酸化物顆粒表面及び開気孔内部に残存する。残存したホウ酸化合物は電池性能に悪影響を及ぼすため、水洗によりホウ素のマンガンに対するモル比で０．０００５未満になるまで除去することが好ましい。
【００２５】
ホウ酸化合物が電池性能に影響しない好ましい範囲はマンガンに対するモル比で０＜Ｂ／Ｍｎ＜０．０００５であり、０＜Ｂ／Ｍｎ＜０．０００３であることがさらに好ましい。
【００２６】
本発明のリチウムマンガン複合酸化物を正極活物質として用いた非水電解質二次電池は優れた放電レート特性を示す。この優れた放電レート特性は、本発明のリチウムマンガン複合酸化物の顆粒二次粒子内に存在する均一な網目状の多数の開気孔からもたらされたものと推定される。すなわち、放電レートはリチウムイオンの正極活物質内での輸送のされ易さに応じて良くなるが、正極活物質が多数の開気孔により網目状組織と化した結果、リチウムイオンの物質内〜外部電解液間の輸送距離が短くなり、輸送が容易になったものと推定される。
【００２７】
【実施例】
以下本発明を実施例により具体的に説明するが、本発明は下記の実施例に限定されるものではない。
【００２８】
実施例１
炭酸リチウム粉末（平均粒子径７μｍ）と電解二酸化マンガン粉末（平均粒子径３μｍ）及びホウ酸を組成Ｌｉ１．１Ｍｎ１．９Ｂ０．０１Ｏ４になるように秤量し、水を適量加えた後、湿式媒体攪拌式ミルで１時間粉砕した。固形分濃度が１５ｗｔ％のスラリーとなるように水を加えて調整し、噴霧乾燥装置により水を蒸発させ、球状の顆粒乾燥粒子を得た。噴霧乾燥は熱風入口温度２５０℃で行った。この乾燥粉末を８５０℃で５時間焼成してリチウムマンガン複合酸化物とした。さらに９５℃温水浴中で１時間洗浄し、濾過後乾燥して試料を得た。
【００２９】
実施例２〜４
実施例１で用いた炭酸リチウム、電解二酸化マンガン、ホウ酸の各粉末以外に添加剤（Ｍ）として、水酸化アルミニウム、酸化クロム、水酸化ニッケルの各粉末を追加して、組成Ｌｉ１．１Ｍ０．１Ｍｎ１．８Ｂ０．０１Ｏ４ （Ｍ＝Ａｌ、Ｃｒ又はＮｉ）となるように秤量した以外は実施例１とまったく同様な方法によって試料を得た。
【００３０】
実施例５
実施例１で用いた炭酸リチウム、電解二酸化マンガン、ホウ酸の各粉末以外に添加剤として弗化リチウムと水酸化アルミニウムの各粉末を追加して、組成Ｌｉ１．０３Ａｌ０．１６Ｍｎ１．８１Ｂ０．００５Ｏ３．８Ｆ０．２ となるように秤量した以外は実施例１とまったく同様な方法によって試料を得た。
【００３１】
実施例６
実施例１で用いた炭酸リチウム、電解二酸化マンガン、ホウ酸の各粉末以外に添加剤として、水酸化アルミニウム各粉末を追加して、組成Ｌｉ１．０８Ａｌ０．１５Ｍｎ１．７８Ｂ０．０１Ｏ４となるように秤量した以外は実施例１とまったく同様な方法によって試料を得た。
【００３２】
実施例７
実施例１で用いた炭酸リチウム、電解二酸化マンガン、ホウ酸の各粉末以外に添加剤として、水酸化アルミニウム各粉末を追加して、組成Ｌｉ１．０１Ａｌ０．３３Ｍｎ１．６７Ｂ０．０１Ｏ４となるように秤量した以外は実施例１とまったく同様な方法によって試料を得た。
【００３３】
実施例８
実施例１で用いた炭酸リチウム、電解二酸化マンガン、ホウ酸の各粉末以外に添加剤として、水酸化アルミニウム各粉末を追加して、組成Ｌｉ１．１２Ａｌ０．０１Ｍｎ１．８８Ｂ０．０１Ｏ４となるように秤量した以外は実施例１とまったく同様な方法によって試料を得た。
【００３４】
実施例９
実施例１で用いた炭酸リチウム、電解二酸化マンガン、ホウ酸の各粉末以外に添加剤として、水酸化アルミニウム各粉末を追加して、組成Ｌｉ１．２Ａｌ０．１Ｍｎ１．８Ｂ０．１０Ｏ４となるように秤量した以外は実施例１とまったく同様な方法によって試料を得た。
【００３５】
実施例１０
実施例１で用いた炭酸リチウム、電解二酸化マンガン、ホウ酸の各粉末以外に添加剤として、水酸化アルミニウム各粉末を追加して、組成Ｌｉ１．１Ａｌ０．１Ｍｎ１．８Ｂ０．００５Ｏ４となるように秤量した以外は実施例１とまったく同様な方法によって試料を得た。
【００３６】
実施例１１
炭酸リチウム粉末（平均粒子径７μｍ）と電解二酸化マンガン粉末（平均粒子径３μｍ）とホウ酸を組成Ｌｉ１．１Ｍｎ１．９Ｂ０．０１Ｏ４になるように秤量し、ジルコニア製ボールを入れたナイロン製ポットに移し、水を適量加えた後、ボールミルで４８時間粉砕した。こうして得たスラリーにさらに水を加えて、固形分濃度１５ｗｔ％になるように調整した。スラリーは２時間放置後でも固液分離を示さず、良好な分散状態を示した。噴霧乾燥装置によりスラリーから水を蒸発させ、球状の乾燥粒子を得た。噴霧乾燥は熱風入口温度２５０℃、出口温度１４０℃で行った。得られた粉末を８５０℃で１０時間焼成し、試料を得た。この試料を塩酸に溶かし、その溶液をＩＣＰを用いて測定し組成分析を行った。ホウ酸化合物を含めた試料の組成はＬｉ１．１Ｍｎ１．９Ｂ０．０１Ｏ４であり、リチウムマンガン系複合酸化物中のマンガンとホウ酸化合物中ホウ素との原子比Ｂ／Ｍｎは０．００５３であった。
【００３７】
実施例１２
実施例１１で用いた炭酸リチウム粉末、電解二酸化マンガン、ホウ酸の各粉末に水酸化アルミニウムを追加して組成Ｌｉ１．１Ａｌ０．１Ｍｎ１．８Ｂ０．０１Ｏ４になるように秤量し添加した以外は、実施例１１と全く同様な操作を行った。得られた試料のホウ酸化合物を含めた組成はＬｉ１．１Ｍｎ１．８Ａｌ０．１Ｂ０．０１Ｏ４であり、リチウムマンガン系複合酸化物中のマンガンとホウ酸化合物中ホウ素との原子比Ｂ／Ｍｎは０．００５６であった。
【００３８】
実施例１３
実施例１１で用いた炭酸リチウム粉末、電解二酸化マンガン、ホウ酸の各粉末に酸化クロムＣｒ２Ｏ３を追加して組成Ｌｉ１．１Ｃｒ０．１Ｍｎ１．８Ｂ０．０１Ｏ４になるように秤量し添加した以外は、実施例１１と全く同様な操作を行った。得られた試料のホウ酸化合物を含めた組成はＬｉ１．１Ｍｎ１．８Ｃｒ０．１Ｂ０．０１Ｏ４であり、リチウムマンガン系複合酸化物中のマンガンとホウ酸化合物中ホウ素との原子比Ｂ／Ｍｎは０．００５６であった。
【００３９】
実施例１４
実施例１１で用いた炭酸リチウム粉末、電解二酸化マンガン、ホウ酸の各粉末に水酸化アルミニウムと弗化リチウムを追加して組成Ｌｉ１．１Ａｌ０．１Ｍｎ１．８Ｂ０．０１Ｏ３．９Ｆ０．１になるように秤量し添加した以外は、実施例１１と全く同様な操作を行った。得られた試料のホウ酸化合物を含めた組成はＬｉ１．１Ａｌ０．１Ｍｎ１．８Ｂ０．０１Ｏ３．９Ｆ０．１であり、リチウムマンガン系複合酸化物中のマンガンとホウ酸化合物中ホウ素との原子比Ｂ／Ｍｎは０．００５６であった。
【００４０】
実施例１５
実施例１２で得られたスピネル型マンガン酸リチウム粉末について、スラリー濃度２０ｗｔ％で水中に懸濁させ、９５℃で６Ｈｒ攪拌した。その後、固形物を濾過・乾燥して試料を得た。得られた試料を塩酸に溶かし、その溶液をＩＣＰを用いて測定し組成分析を行った。ホウ酸化合物を含めた試料の組成はＬｉ１．１Ｍｎ１．８Ａｌ０．１Ｂ０．０００４であり、リチウムマンガン系複合酸化物中のマンガンとホウ酸化合物中ホウ素との原子比Ｂ／Ｍｎは０．０００２２であった。
【００４１】
比較例１
炭酸リチウム粉末を水酸化リチウム一水和物（ＬｉＯＨ・Ｈ２Ｏ）粉末に代えた以外は実施例１とまったく同様の方法によって試料を得た。なお、水酸化リチウム一水和物は噴霧乾燥前のスラリー中では水に完全に溶解した状態であった。
【００４２】
比較例２〜４
炭酸リチウム粉末を水酸化リチウム一水和物（ＬｉＯＨ・Ｈ２Ｏ）粉末に代えた以外は実施例２〜４とまったく同様の方法によって試料を得た。なお、水酸化リチウム一水和物は噴霧乾燥前のスラリー中では水に完全に溶解した状態であった。
【００４３】
比較例５
炭酸リチウム粉末を水酸化リチウム一水和物（ＬｉＯＨ・Ｈ２Ｏ）粉末に代えた以外は実施例５とまったく同様の方法によって試料を得た。なお、水酸化リチウム一水和物は噴霧乾燥前のスラリー中では水に完全に溶解した状態であった。
【００４４】
比較例６
電解二酸化マンガン（平均粒子径１５μｍ）と炭酸リチウム（平均粒子径３μｍ）の各粉末を組成Ｌｉ１．１２Ｍｎ１．８８Ｏ４になるように秤量し、乾式混合した後、９００℃で１２時間焼成しリチウムマンガン複合酸化物となった試料を得た。
【００４５】
実施例１６
実施例１で噴霧乾燥に用いたスラリーに含まれる二酸化マンガンと炭酸リチウム混合粉末の粒度をレーザー回折散乱粒度計で測定した結果、平均体積粒子径は０．６５μｍであり、粒度分布の広さを示す標準偏差は０．０７であった。
【００４６】
実施例１７
実施例１〜１０、比較例１〜５及び比較例６の試料について、組成を化学分析により、比表面積をＢＥＴ測定装置により、顆粒二次粒子の平均径をレーザー回折散乱粒度計により、顆粒を構成する結晶一次粒子の平均径を走査型電子顕微鏡観察により求め、表１の結果を得た。
【００４７】
【表１】
実施例１〜１０、比較例１〜５及び比較例６の試料について、顆粒二次粒子の断面写真を走査型電子顕微鏡により撮影した。この際、粉末を硬化性樹脂に埋め込み、表面研磨によって顆粒の切断面を露出させたものを撮影試料とした。電顕写真の画像解析処理を行い、顆粒二次粒子内に存在する開気孔の平均径と量を求め、表２の結果を得た。顆粒切断面の電顕写真（実施例２、比較例２及び比較例６）の例を図１〜３に示す。なお、開気孔平均径は気孔数５００〜１０００個について個数平均値を採った。
【００４８】
【表２】
実施例１１〜１４で得られたスラリーの少量をメタノール中に入れ、超音波により分散し、粒子径分布をレーザー回折散乱法にて測定した。スラリーを構成する粉末の平均体積粒子径として表３の結果を得た。粒度分布の広さを示す標準偏差はいすれも０．５程度であった。次に、実施例１１〜１５で得られた試料について、１０ｇをメスシリンダーに入れ、５０回振動前後の体積を測定し、粉末の嵩密度を求めた。また、平均粒子径を上述の測定法で求めた。結果を表３に併せて示す。さらに、実施例１１〜１５で得られた試料の組織を走査型電子顕微鏡で観察した結果、いずれも結晶一次粒子は１〜５μｍの大きさであり平均粒子径は約２μｍであった。顆粒二次粒子の平均径は約２０μｍであり、球状であった。
【００４９】
【表３】
実施例１１および１２で得られた試料と導電剤／結着剤（アセチレンブラック／テフロン（登録商標））を混合して正極物質とし、負極物質として金属リチウムを、電解液としてＬｉＰＦ６を溶解させたエチレンカーボネート／ジメチルカーボネート溶液を用いコインセル型電池を作成した。充放電試験は６０℃で電流密度０．４ｍＡ／ｃｍ２、電圧４．３〜３．０Ｖの範囲で行った。サイクル維持率を１０回目と５０回目の放電容量の差から求め表４の結果を得た。
【００５０】
【表４】
実施例１〜１０、比較例１〜５及び比較例６の試料について、放電レート特性を測定した。各試料粉末と導電剤／結着剤（アセチレンブラック／テフロン（登録商標）系樹脂）を混合して正極活物質とし、負極活物質として金属リチウムを、電解液としてＬｉＰＦ６を溶解させたエチレンカーボネート／ジメチルカーボネート溶液を用いコインセル型電池を作成した。これらの電池について室温にて放電レートを測定した。測定結果の例を図４に示す。また、すべての試料についてレート維持率（０．３Ｃでの放電容量を基準としたときの５．５Ｃでの放電容量の比率）と放電容量を表５に示す。実施例１〜１０の試料は比較例１〜５及び比較例６の試料に比べて優れた放電レート特性であることが明確である。
【００５１】
【表５】
【図面の簡単な説明】
【図１】実施例２における試料の顆粒二次粒子の断面を示す図である。
【図２】比較例２における試料の顆粒二次粒子の断面を示す図である。
【図３】比較例６における試料の顆粒二次粒子の断面を示す図である。
【図４】実施例２、比較例２及び比較例６における試料の放電レート特性を示す図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a lithium manganese composite oxide powder, a method for producing the same, and a non-aqueous electrolyte secondary battery that is a use thereof.
[0002]
[Prior art]
When a lithium manganese composite oxide is used as a positive electrode active material of a non-aqueous electrolyte secondary battery, a powder composed of granular secondary particles of an appropriate size obtained by sintering primary crystal particles is used. Conventionally, several methods have been applied to the production of granular secondary particles. For example, Japanese Patent Application Laid-Open No. 2000-169151 discloses that when a lithium manganese composite oxide is obtained from the reaction between electrolytic manganese dioxide and lithium carbonate, the size of electrolytic manganese dioxide, which is a starting material, is adjusted by pulverization, so that even after the reaction, Japanese Patent Application Laid-Open No. 10-172567 discloses a method for forming secondary particles having a large size. Japanese Patent Application Laid-Open No. 10-172567 discloses a method in which a slurry in which an electrolytic manganese dioxide powder is dispersed in an aqueous solution of a water-soluble lithium compound is spray-dried, granulated, and granulated. JP-A-10-228515 and JP-A-10-297924 disclose a method of compacting and agglomerating a fine powder using a roller compactor or the like to form secondary particles. Have been.
[0003]
As is known from these disclosures, conventionally, from the viewpoint of increasing the discharge capacity per volume of the battery, emphasis has been placed on making the granular secondary particles as dense as possible and increasing the packing density of the powder. Therefore, there have been few examples in which the structure of granular secondary particles, particularly the pores therein, has been characterized.
[0004]
Japanese Patent Application Laid-Open No. 2002-75365 describes, for example, those that characterize the pores inherent in the granular secondary particles. This is intended to provide a positive electrode active material having excellent high rate charge / discharge characteristics and cycle characteristics by forming pores inside the particles of the positive electrode active material. However, since these pores are closed, and the pores are not communicated with the external environment of the particles, diffusion of lithium ions into the electrolyte is not sufficiently performed, and improvement of high rate characteristics and cycle characteristics is insufficient. Was something. That is, in Table 2 on page 5 of the above publication, the high-rate charge / discharge characteristics are evaluated based on the ratio between the capacity when 2.0 coulombs are supplied and the capacity when 0.2 coulombs are supplied. % Or less, which is insufficient for high-rate charge / discharge characteristics.
[0005]
[Problems to be solved by the invention]
The present invention has an object of controlling the structure of secondary particles of a lithium manganese composite oxide, and has been made by paying particular attention to the form of open pores in the granules. An object of the present invention is to provide a lithium-manganese composite oxide positive electrode active material suitable as a constituent material of a non-aqueous electrolyte secondary battery exhibiting high output characteristics, and a method for producing the same.
[0006]
[Means for Solving the Problems]
In the present invention, the size and amount of open pores present in the granular secondary particles of the lithium manganese composite oxide are determined by the discharge rate characteristics of a non-aqueous electrolyte secondary battery using this oxide as a positive electrode active material (JP-A-2002-75365). It has been achieved by finding that it is a factor that governs the high-rate charge / discharge characteristics in the publication (corresponding characteristics). That is, the secondary particles of the lithium manganese composite oxide granules of the present invention have a large number of micrometer-sized open pores in the form of a mesh in the particles, and the size of the pores is in the range of 0.5 to 3 μm as an average diameter. And the amount is an average of 3 to 20 vol. %.
[0007]
The greatest feature is that a large number of micrometer-sized open pores are present in the form of a mesh in the secondary particles of granules (hereinafter sometimes simply referred to as "granules"). As a result, the discharge rate characteristics of the battery can be improved.
[0008]
The open pore of micrometer size is defined by size and amount, the size is 0.5 to 3 μm as an average diameter, and the amount is 3 to 20 vol. %. If the average diameter of the pores is less than 0.5 μm, the discharge rate characteristics of the battery deteriorate. In addition, when the pore size exceeds 3 μm, it becomes difficult to maintain the strength of the granules. The most preferred average diameter is in the range of 1.0-2.5 μm.
[0009]
The ratio of open pores was 3 vol. %, The discharge rate characteristics of the battery deteriorate, and 20 vol. %, It becomes difficult to secure a high powder packing density required as an electrode material. The most preferable ratio of open pores is 5 to 15 vol. %.
[0010]
The average diameter and amount of the open pores are values obtained by approximating the open pores spherically, and as a measuring method, a scanning electron micrograph of a cut surface of the granule is taken and can be known by a method of image analysis processing. Here, the number average value obtained from the average of 500 or more pores is used.
[0011]
In addition to having a large number of open pores, the granular secondary particles of the present invention have a specific surface area of 0.2 to 1.0 m 2 / g, an average diameter of the granular secondary particles of 5 to 30 μm, and an average diameter of the crystalline primary particles constituting the granules. Is 0.5 to 4.0 μm. These values are specified to maximize the performance of the secondary battery as the positive electrode active material. For example, when the specific surface area exceeds 1.0 m 2 / g or the primary crystal particle diameter is less than 0.5 μm, the cycle deterioration of the charge / discharge capacity becomes remarkable at a temperature of 50 ° C. or more. If it is less than 2 / g, or if it exceeds the crystal primary particle diameter of 4.0 μm, the discharge rate characteristics will deteriorate, which is not preferable. If the average diameter of the secondary particles of the granules is out of the range of 5 to 30 μm, it becomes inconvenient for forming the sheet electrode, and is not appropriate.
[0012]
Lithium-manganese composite oxide of the present invention, preferably, in the composition formula Li X M Y Mn 3-X -Y O 4-Z F Z ( wherein, X = 1.0~1.2, Y = 0~0 .3, Z = 0 to 0.3, M: at least one element selected from Al, Co, Ni, Cr, Fe and Mg). In determining charge / discharge capacity and charge / discharge repetition stability, the Li content X and the content Y of the additional element M are important, and particularly preferable ranges are X = 1.05 to 1.15 and Y = 0.05 to 0.25, X + Y = 1.15 to 1.30 are selected.
[0013]
If the boric acid compound is present in a certain amount or more on the surface of the granules and inside the open pores, the battery performance is adversely affected. A preferable range in which the boric acid compound does not affect the battery performance is 0 <B / Mn <0.0005, and more preferably 0 <B / Mn <0.0003, as a molar ratio to manganese.
[0014]
The method for producing a powder of the present invention comprises granulating a slurry in which a fine powder of manganese oxide and a fine powder of lithium carbonate are dispersed by spray drying, followed by firing at a temperature of 700 to 900 ° C. A slurry in which the powder, the lithium raw material, and the open pore forming agent are dispersed is granulated by spray drying, and then fired at a temperature of 700 to 900C.
[0015]
Examples of the manganese oxide powder include electrolytic manganese dioxide, chemically synthesized manganese dioxide, Mn 3 O 4 , and Mn 2 O 3 .
[0016]
Examples of the lithium source include water-soluble lithium hydroxide or lithium nitrate, and water-insoluble lithium carbonate. When lithium carbonate insoluble in water is used as a lithium source, the lithium carbonate also functions as an open pore forming agent, so that the particle size of lithium carbonate and manganese oxide is important as a factor controlling the pore size. The particle size is suitably on the order of submicron, and the average particle diameter of the mixed powder of lithium carbonate and manganese oxide is preferably 1 μm or less, more preferably 0.3 to 0.7 μm. Such a particle size can be easily attained by putting manganese oxide powder and lithium carbonate powder in water, pulverizing and mixing. As a pulverizing and mixing device, a ball mill, a vibration mill, a wet medium stirring type mill or the like can be used.
[0017]
When it is desired to increase the total volume of the open pores, an open pore preparation other than lithium carbonate may be added.
[0018]
In addition to lithium carbonate, water-soluble lithium hydroxide, lithium nitrate, or the like can be used as the lithium source.
[0019]
In this case, an open pore forming agent must be used, and the particle size is important as a factor controlling the pore size. The particle size is suitably on the submicron order, specifically, preferably 1 μm or less, more preferably in the range of 0.3 to 0.7 μm. Such a particle size can be easily achieved by putting the manganese oxide powder, the lithium raw material and the open pore forming agent powder in water, and pulverizing and mixing. As a pulverizing and mixing device, a ball mill, a vibration mill, a wet medium stirring type mill or the like can be used.
[0020]
As the open pore forming agent, a substance that disappears by heating, such as carbon black, carbon nanotube, and graphite, is used.
[0021]
The amount of pores can be controlled by the amount of the open pore forming agent and the amount of lithium carbonate. The average porosity is 3 to 20 vol. % Is preferable, and 5 to 15 vol. % Is most preferred.
[0022]
The slurry obtained by the wet pulverization and mixing is granulated by spray drying. Spray drying can be performed by a usual spray drier which sprays the slurry with a rotating disk or a fluid nozzle and dries the droplets with hot air. As a granulation method, a method other than spray drying, such as a submerged granulation method and a tumbling granulation method, can be applied, but spray drying is most industrially advantageous.
[0023]
For the purpose of enhancing the performance of the lithium-manganese composite oxide of the present invention as a secondary positive electrode material, manganese, a compound of an element other than lithium, for example, a compound such as aluminum or chromium is often added as an additive element. When the additional element M is added, it is preferable to add the element in the form of an oxide of the element or a precursor thereof (hydroxide or the like). Is appropriate.
[0024]
The addition of the boron compound according to claim 11 is performed for the purpose of controlling the shape of the primary crystal particles of the lithium manganese composite oxide. Thereby, uniform meshing of the open pores is achieved. As the boron compound, H 3 BO 3, B 2 O 3 and Li 2 O · nB 2 O 3 (n = 1 to 5) can be used. It is appropriate to put it in the slurry. The amount of addition is in the range of 0.0005 to 0.05, preferably in the range of 0.01 to 0.001, in terms of molar ratio to manganese. After firing, the boron compound remains as a boric acid compound on the surface of the composite oxide granules and inside the open pores. Since the remaining boric acid compound has a bad effect on battery performance, it is preferable to remove the remaining boric acid compound by water washing until the molar ratio of boron to manganese becomes less than 0.0005.
[0025]
A preferable range in which the boric acid compound does not affect the battery performance is 0 <B / Mn <0.0005, and more preferably 0 <B / Mn <0.0003, as a molar ratio to manganese.
[0026]
The nonaqueous electrolyte secondary battery using the lithium manganese composite oxide of the present invention as a positive electrode active material shows excellent discharge rate characteristics. This excellent discharge rate characteristic is presumed to be caused by a large number of uniform network-like open pores present in the secondary particles of the lithium manganese composite oxide of the present invention. In other words, the discharge rate is improved in accordance with the ease of transport of lithium ions in the positive electrode active material. However, as a result of the positive electrode active material being formed into a network structure by a large number of open pores, the inside of the lithium ion material is It is presumed that the transport distance between the electrolytes became shorter, and transport became easier.
[0027]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples.
[0028]
Example 1
Lithium carbonate powder (average particle diameter: 7 μm), electrolytic manganese dioxide powder (average particle diameter: 3 μm), and boric acid are weighed so as to have a composition of Li 1.1 Mn 1.9 B 0.01 O 4 , and an appropriate amount of water is added. After that, the mixture was pulverized for 1 hour by a wet medium stirring mill. Water was added to adjust the slurry to a solid concentration of 15 wt%, and the water was evaporated using a spray dryer to obtain spherical granulated dry particles. Spray drying was performed at a hot air inlet temperature of 250 ° C. The dried powder was fired at 850 ° C. for 5 hours to obtain a lithium manganese composite oxide. The sample was further washed in a 95 ° C. hot water bath for 1 hour, filtered and dried to obtain a sample.
[0029]
Examples 2 to 4
In addition to the lithium carbonate, electrolytic manganese dioxide, and boric acid powders used in Example 1, aluminum hydroxide, chromium oxide, and nickel hydroxide powders were added as additives (M) to obtain a composition Li 1.1 A sample was obtained in exactly the same manner as in Example 1, except that the sample was weighed so as to be M 0.1 Mn 1.8 B 0.01 O 4 (M = Al, Cr or Ni).
[0030]
Example 5
In addition to the lithium carbonate, electrolytic manganese dioxide, and boric acid powders used in Example 1, lithium fluoride and aluminum hydroxide powders were added as additives to make the composition Li 1.03 Al 0.16 Mn 1. A sample was obtained in exactly the same manner as in Example 1 except that the sample was weighed so as to obtain 81 B 0.005 O 3.8 F 0.2 .
[0031]
Example 6
In addition to the lithium carbonate, electrolytic manganese dioxide, and boric acid powders used in Example 1, aluminum hydroxide powders were added as additives to make the composition Li 1.08 Al 0.15 Mn 1.78 B 0. A sample was obtained in exactly the same manner as in Example 1 except that the sample was weighed so as to be 01 O 4 .
[0032]
Example 7
In addition to the lithium carbonate, electrolytic manganese dioxide, and boric acid powders used in Example 1, aluminum hydroxide powders were added as additives to make the composition Li 1.01 Al 0.33 Mn 1.67 B 0. A sample was obtained in exactly the same manner as in Example 1 except that the sample was weighed so as to be 01 O 4 .
[0033]
Example 8
In addition to the lithium carbonate, electrolytic manganese dioxide, and boric acid powders used in Example 1, aluminum hydroxide powders were added as additives to make the composition Li 1.12 Al 0.01 Mn 1.88 B 0. A sample was obtained in exactly the same manner as in Example 1 except that the sample was weighed so as to be 01 O 4 .
[0034]
Example 9
In addition to the lithium carbonate, electrolytic manganese dioxide, and boric acid powders used in Example 1, aluminum hydroxide powders were added as additives to make the composition Li 1.2 Al 0.1 Mn 1.8 B 0.8. A sample was obtained in exactly the same manner as in Example 1, except that the sample was weighed to 10 O 4 .
[0035]
Example 10
In addition to the lithium carbonate, electrolytic manganese dioxide, and boric acid powders used in Example 1, aluminum hydroxide powders were added as additives to make the composition Li 1.1 Al 0.1 Mn 1.8 B 0.8. A sample was obtained in exactly the same manner as in Example 1 except that the sample was weighed to be 005 O 4 .
[0036]
Example 11
Lithium carbonate powder (average particle diameter: 7 μm), electrolytic manganese dioxide powder (average particle diameter: 3 μm), and boric acid were weighed so as to have a composition of Li 1.1 Mn 1.9 B 0.01 O 4 , and a zirconia ball was prepared. After being transferred to a nylon pot containing the water and adding an appropriate amount of water, the mixture was ground by a ball mill for 48 hours. Water was further added to the slurry thus obtained to adjust the solid content to 15 wt%. The slurry did not show solid-liquid separation even after standing for 2 hours, and showed a good dispersion state. Water was evaporated from the slurry by a spray dryer to obtain spherical dry particles. The spray drying was performed at a hot air inlet temperature of 250 ° C and an outlet temperature of 140 ° C. The obtained powder was fired at 850 ° C. for 10 hours to obtain a sample. This sample was dissolved in hydrochloric acid, and the solution was measured using ICP to analyze the composition. The composition of the sample including the borate compound is Li 1.1 Mn 1.9 B 0.01 O 4 , and the atomic ratio B / Mn of manganese in the lithium manganese-based composite oxide and boron in the borate compound is: 0.0053.
[0037]
Example 12
Aluminum hydroxide was added to each of the lithium carbonate powder, electrolytic manganese dioxide, and boric acid powder used in Example 11 so that the composition became Li 1.1 Al 0.1 Mn 1.8 B 0.01 O 4. Except for the weighing and addition, the same operation as in Example 11 was performed. The composition of the obtained sample including the boric acid compound was Li 1.1 Mn 1.8 Al 0.1 B 0.01 O 4 , and manganese in the lithium manganese-based composite oxide and boron in the boric acid compound were Was 0.0056 in atomic ratio B / Mn.
[0038]
Example 13
Chromium oxide Cr 2 O 3 was added to each of the lithium carbonate powder, electrolytic manganese dioxide, and boric acid powder used in Example 11 to obtain a composition Li 1.1 Cr 0.1 Mn 1.8 B 0.01 O 4 . The same operation as in Example 11 was performed except that the sample was weighed and added. The composition of the obtained sample including the boric acid compound was Li 1.1 Mn 1.8 Cr 0.1 B 0.01 O 4 , and manganese in the lithium manganese-based composite oxide and boron in the boric acid compound were Was 0.0056 in atomic ratio B / Mn.
[0039]
Example 14
Aluminum hydroxide and lithium fluoride were added to each of the lithium carbonate powder, electrolytic manganese dioxide, and boric acid powder used in Example 11, and the composition was Li 1.1 Al 0.1 Mn 1.8 B 0.01 O 3. except for adding weighed so as to .9 F 0.1 were conducted in exactly the same manner as in example 11. The composition of the obtained sample including the boric acid compound was Li 1.1 Al 0.1 Mn 1.8 B 0.01 O 3.9 F 0.1 , and the content of manganese in the lithium manganese-based composite oxide was reduced to The atomic ratio B / Mn with boron in the boric acid compound was 0.0056.
[0040]
Example 15
The spinel-type lithium manganate powder obtained in Example 12 was suspended in water at a slurry concentration of 20 wt% and stirred at 95 ° C. for 6 hours. Thereafter, the solid was filtered and dried to obtain a sample. The obtained sample was dissolved in hydrochloric acid, and the solution was measured using ICP to analyze the composition. The composition of the sample including the borate compound was Li 1.1 Mn 1.8 Al 0.1 B 0.0004 , and the atomic ratio B / of manganese in the lithium manganese-based composite oxide to boron in the borate compound was Mn was 0.00022.
[0041]
Comparative Example 1
A sample was obtained in exactly the same manner as in Example 1, except that the lithium carbonate powder was replaced with lithium hydroxide monohydrate (LiOH.H 2 O) powder. Note that lithium hydroxide monohydrate was completely dissolved in water in the slurry before spray drying.
[0042]
Comparative Examples 2 to 4
Samples were obtained in exactly the same manner as in Examples 2 to 4, except that the lithium carbonate powder was replaced with lithium hydroxide monohydrate (LiOH.H 2 O) powder. Note that lithium hydroxide monohydrate was completely dissolved in water in the slurry before spray drying.
[0043]
Comparative Example 5
A sample was obtained in exactly the same manner as in Example 5, except that the lithium carbonate powder was replaced with lithium hydroxide monohydrate (LiOH.H 2 O) powder. Note that lithium hydroxide monohydrate was completely dissolved in water in the slurry before spray drying.
[0044]
Comparative Example 6
Each powder of electrolytic manganese dioxide (average particle diameter: 15 μm) and lithium carbonate (average particle diameter: 3 μm) was weighed so as to have a composition of Li 1.12 Mn 1.88 O 4 , dry-mixed, and then mixed at 900 ° C. for 12 hours. A sample which was fired to form a lithium manganese composite oxide was obtained.
[0045]
Example 16
As a result of measuring the particle size of the mixed powder of manganese dioxide and lithium carbonate contained in the slurry used for spray drying in Example 1 with a laser diffraction scattering particle size meter, the average volume particle size was 0.65 μm, and the width of the particle size distribution was The standard deviation shown was 0.07.
[0046]
Example 17
For the samples of Examples 1 to 10, Comparative Examples 1 to 5 and Comparative Example 6, the composition was analyzed by chemical analysis, the specific surface area was measured by a BET measuring device, and the average diameter of the secondary particles of the granules was measured by a laser diffraction scattering granulometer. The average diameter of the constituent primary crystal particles was determined by scanning electron microscope observation, and the results shown in Table 1 were obtained.
[0047]
[Table 1]
For the samples of Examples 1 to 10, Comparative Examples 1 to 5, and Comparative Example 6, cross-sectional photographs of the secondary particles of the granules were taken with a scanning electron microscope. At this time, the powder was embedded in a curable resin, and the cut surface of the granules exposed by surface polishing was used as a photographing sample. Image analysis of electron micrographs was performed to determine the average diameter and amount of open pores present in the secondary particles of the granules, and the results in Table 2 were obtained. Examples of electron micrographs (Example 2, Comparative Example 2, and Comparative Example 6) of the cut surface of the granules are shown in FIGS. The average diameter of the open pores was the number average value of 500 to 1000 pores.
[0048]
[Table 2]
A small amount of the slurries obtained in Examples 11 to 14 was put in methanol, dispersed by ultrasonic waves, and the particle size distribution was measured by a laser diffraction scattering method. The results shown in Table 3 were obtained as the average volume particle diameter of the powder constituting the slurry. The standard deviation indicating the breadth of the particle size distribution was about 0.5. Next, 10 g of the samples obtained in Examples 11 to 15 were put in a measuring cylinder, and the volume before and after 50 times of vibration was measured to determine the bulk density of the powder. Further, the average particle size was determined by the above-described measurement method. The results are shown in Table 3. Further, as a result of observing the structures of the samples obtained in Examples 11 to 15 with a scanning electron microscope, the crystal primary particles were all 1 to 5 μm in size and the average particle diameter was about 2 μm. The average diameter of the secondary particles of the granules was about 20 μm, and the particles were spherical.
[0049]
[Table 3]
The samples obtained in Examples 11 and 12 and a conductive agent / binder (acetylene black / Teflon (registered trademark)) were mixed to form a positive electrode material, metallic lithium was dissolved as a negative electrode material, and LiPF 6 was dissolved as an electrolytic solution. A coin cell battery was prepared using the ethylene carbonate / dimethyl carbonate solution. The charge / discharge test was performed at 60 ° C. with a current density of 0.4 mA / cm 2 and a voltage of 4.3 to 3.0 V. The cycle retention was determined from the difference between the discharge capacities at the 10th and 50th discharges, and the results in Table 4 were obtained.
[0050]
[Table 4]
The discharge rate characteristics of the samples of Examples 1 to 10, Comparative Examples 1 to 5, and Comparative Example 6 were measured. Ethylene carbonate prepared by mixing each sample powder with a conductive agent / binder (acetylene black / Teflon (registered trademark) resin) to form a positive electrode active material, lithium metal as a negative electrode active material, and LiPF 6 as an electrolyte solution / Dimethyl carbonate solution was used to prepare a coin cell type battery. The discharge rates of these batteries were measured at room temperature. FIG. 4 shows an example of the measurement result. Table 5 shows the rate retention ratio (the ratio of the discharge capacity at 5.5 C based on the discharge capacity at 0.3 C) and the discharge capacity for all the samples. It is clear that the samples of Examples 1 to 10 have better discharge rate characteristics than the samples of Comparative Examples 1 to 5 and Comparative Example 6.
[0051]
[Table 5]
[Brief description of the drawings]
FIG. 1 is a view showing a cross section of a granular secondary particle of a sample in Example 2.
FIG. 2 is a view showing a cross section of a granular secondary particle of a sample in Comparative Example 2.
FIG. 3 is a diagram showing a cross section of a granular secondary particle of a sample in Comparative Example 6.
FIG. 4 is a diagram showing discharge rate characteristics of samples in Example 2, Comparative Examples 2 and 6.
Claims (12)
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