CN1171638A - 锂电池用正极活性物质、制造方法及含该活性物质的锂电池 - Google Patents
锂电池用正极活性物质、制造方法及含该活性物质的锂电池 Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000011149 active material Substances 0.000 claims description 26
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 12
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 11
- 239000000428 dust Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910013553 LiNO Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 claims description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims description 2
- 229910003174 MnOOH Inorganic materials 0.000 claims description 2
- RISRGKINPSVAJP-UHFFFAOYSA-N [Li].C(CCC)(=O)O Chemical compound [Li].C(CCC)(=O)O RISRGKINPSVAJP-UHFFFAOYSA-N 0.000 claims description 2
- BLMXJJXSWRYMCS-UHFFFAOYSA-L butanoate;manganese(2+) Chemical compound [Mn+2].CCCC([O-])=O.CCCC([O-])=O BLMXJJXSWRYMCS-UHFFFAOYSA-L 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 229940097206 manganese citrate Drugs 0.000 claims description 2
- 235000014872 manganese citrate Nutrition 0.000 claims description 2
- 239000011564 manganese citrate Substances 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 2
- 239000011651 chromium Substances 0.000 claims 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- 229910001339 C alloy Inorganic materials 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 150000002641 lithium Chemical class 0.000 claims 1
- 229910001092 metal group alloy Inorganic materials 0.000 claims 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910014689 LiMnO Inorganic materials 0.000 description 27
- 239000012071 phase Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910013292 LiNiO Inorganic materials 0.000 description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 5
- -1 oxonium ion Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910015645 LiMn Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000003746 solid phase reaction Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910032387 LiCoO2 Inorganic materials 0.000 description 3
- 229910003005 LiNiO2 Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 229910006290 γ-MnOOH Inorganic materials 0.000 description 3
- 244000309464 bull Species 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052705 radium Inorganic materials 0.000 description 2
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- CVOFKRWYWCSDMA-UHFFFAOYSA-N 2-chloro-n-(2,6-diethylphenyl)-n-(methoxymethyl)acetamide;2,6-dinitro-n,n-dipropyl-4-(trifluoromethyl)aniline Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl.CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O CVOFKRWYWCSDMA-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010888 waste organic solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 1
- 229910006596 α−NaFeO2 Inorganic materials 0.000 description 1
- 229910006287 γ-MnO2 Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/36—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions
- C01B13/366—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions by hydrothermal processing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
锂电池用廉价的正极活性物质包含具有六方晶系多层结构的锰酸锂,其空间群为R3m且对于金属锂能显示出从4.5V到2V的连续放电电压特性。
Description
本发明涉及锂电池用正极活性物质，制造方法以及在正极中含该活性物质的电池。
由于近来轻便型电器的发展，一直需要高性能的电池。锂离子电池作为非水溶液电池，具有高工作电压和高能密度，在其负极使用碳质材料，在其正极使用具有层状结构的复合氧化物钴酸锂(LiCoO2)，这种锂离子电池一直在投入使用。镍酸锂(含锂的氧化镍；LiNiO2)也是一种有着与钴酸锂同样多层晶体结构的化合物，其中锂离子被插在共用晶棱的NiO6八面体层之间。
通常制备镍酸锂是通过混合选自Ni(NO3)2、Ni(OH)2、NiCO3、NiO、NiOOH等的镍源与选自LiOH、LiNO3、Li2CO3、Li2O2等的锂，再于约600-900℃下在氧气流中使混合物经过热处理。
用在这些活性物质上的钴或镍因原料缺乏而价格昂贵，所以人们一直在寻找正极用价格便宜的活性物质。例如，早已提出使用具有尖晶石结构的含Li锰复合氧化物(LiMnO4)，然而它的理论容量148mAh/g是低的，且重复进行充电/放电循环时容量还下降。
LiMnO2一直作为高性能电池用最有前途的活性物质被提出。在由LiMnO2显示的多种晶相中，有两种晶相，具有明显区别的晶体结构，一种是高温正交晶相(Pmnm)，一种是低温四方晶相(I41/amd)。这两种结构都有立方密堆积，但在锂和锰阳离子排列次序的分布上不同。制备四方晶型Li2Mn2O4是用电化学或化学方法把锂插入尖晶石LiMn2O4中(“材料研究公报”(Mat.Res.Bull)，1983年第18期第461页和1983年第18期第1375页；“电化学学会杂志”(J.Electrochem.Soc.)，1991年第138期第2864页和1992年第139期第937页)。制备正交晶相主要通过用不同的前体在高温下进行固相反应[“固体物理化学杂志”(J.Phys.Chem.Solid)，1957年第3期第20页和第318页；“镭物理杂志(J.Phys.Radium)，1959年第20期第155页；“普通无机化学杂志”(J.Anorg.Allg.Chem.)，1975年第417期第1页；“材料研究公报”(Mater.Res.Bull)，1993年第28期第1249页]。然而发表的正交晶系LiMnO2是通过把γ-MnOOH和LiOH的混合物加热到300-450℃利用低温下的固态反应制备的[“化学快讯”(Chem.Express)，1992年第7期第193页]。还发表了另外制备正交晶系LiMnO2的方法是在低于100℃的温度下通过离子交换完成的[“电化学学会杂志”(J.Electrochem.Soc.)，1993年第140期第3396页；未审查的日本专利公告1994-349494]。在这种情况下，交换是通过γ-MnOOH在LiOH溶液中沸腾条件下回流完成的。到现在为止，与多层LiNiO2或LiCoO2异构的LiMnO2尚未合成出来。
对于层状结构的LiMnO2，“固体化学杂志”(J.Solid State Chem.)，1993年第104期第464页和美国专利5,153,081发表了单斜晶系层状结构的LiMnO2可通过酸排除Li2MnO3中的LiO2获得。首先，通过电解二氧化锰(EMD)与化学计量的Li2O3反应制备Li2MnO3。所得到的物质在室温下用H2SO4脱氧化锂64小时。
如此得到的物质对Li/Li+可显示3V的放电电压特性。尽管反应产物在2θ＝19.5°的地方显示新的X-射线衍射峰，但是大多数别的峰值却与原料Li2MnO3相当(美国专利5,153,081)。不管指定原料Li2MnO3峰与大多数峰相同这一事实，美国专利5,153,081的发明人鉴定产物就是基于2θ＝19.5°处峰具有层状结构的物质，然而这种鉴定似乎有决定性不合理的地方。既然是这样，产物倒不如按基本骨架被认定为具有尖晶石结构的锂锰氧化物，如Li2Mn4O9或Li4Mn5O12。
此外，“固体化学杂志”(J.Solid State Chem.)1993年第104期第464页发表了一种具有层状结构的物质，其X-射线衍射图不同于LiNiO2或LiCoO2的衍射图。尽管没有涉及这种物质结构改进的细节，但是基于其多层结构的这篇报告在假定从Li2MnO3中除去Li2O的情况下能使密堆积的氧平面切变而引起氧在所获得的物质中排列，该物质由固定锂的三方柱轮换层和固定锰的共用晶棱层组成。在这种情况下，锰离子在排除过程中仍保留在轮换层中而不迁移到锂层中，而锂层在锂离子以三方柱配位时按曲折形式排列。
未审查日本专利公开1995-223819报导通过电解方法可以得到具有层状结构的LiMnO2，其晶胞常数a＝3.321埃和c＝4.730埃。这种物质与LiNiO2不异构。因此，尚未合成出与LiNiO2或LiCoO2相同的层状结构LiMnO2。
如上所述，尽管已经建议具有尖晶石结构的4.0V型LiMn2O4可作为廉价含Li的锰复合氧化物，但其理论容量不如具有六方层状结构的氧化物化合物，如LiNiO2(理论容量：275mAh/g)和LiCoO2(理论容量：274mAh/g)。此外，充电/放电循环特性优于多层氧化物材料。由此，迫切要求开发出具有类似于LiNiO2或LiCoO2层状结构的廉价活性物质以及确定其合成方法，但有效的合成方法尚未形成。
本发明的目的是制备具有与已知LiMn2O4尖晶石结构不同而与钴酸锂或镍酸锂六方层状结构类似的锰酸锂，具有R3m的空间群，由此期望锰酸锂作为锂电池用的正极活性物质能显示提高的活性。
本发明提供一种锂电池用的正极活性物质，它含有六方层状结构的锰酸锂，其空间群为R3m，对Li/Li+能显示介于4.5V-2V的连续放电电压特性。本发明的活性物质理论容量为286mAh/g。
本发明还提供一种生产这种正极活性物质的方法，以及含有这种正极活性物质的电池。
本发明的正极活性物质经过均相反应以致对Li/Li+能显示介于4.5V-2.0V的连续放电电压特性。循环时放电特性是稳定的，因而提供了使用期长的电池。本发明的活性物质廉价而经济。
图1A表明具有本发明层状结构的LiMnO2 X-射线衍射图；
图1B表明具有层状结构的LiNiO2 X-射线衍射图；
图1C表明具有由常规固相反应获得的正交结构LiMnO2的X-射线衍射图；
图2表明本发明LiMnO2层状结构的图解说明；和
图3表明本发明LiMnO2的典型放电特性曲线。
本发明的锰酸锂不是由γ-MnOOH与LiOH以固相煅烧法反应获得的已知LiMnO2，而是由γ-MnO2在LiOH溶液中水热反应获得的LiMnO2，其层状结构与LiNiO2或LiCoO2的结构相似。本发明的锰酸锂可以非水溶液的形式作为正极活性物质使用，以便提供便宜且高效的电池。
本发明的活性物质具有与LiNiO2或LiCoO2结构相似的层状结构，即与α-NaFeO2相似的结构。
活性物质的结构描述依据是堆积的MnO2片是由共用晶棱的MnO6八面体组成，锂离子位于八面体氧围绕的八面体中间。这种结构包括由按立方密堆积排列形式排列的氧离子围绕成八面体包围的锰离子层，从而导致共用晶棱的八面体片的形成。还包括锂层，锂在锂层呈八面体包围并夹在两层八面体MnO6之间。
发现本发明的活生物质具有与LiNiO2或LiCoO2相似的层状结构，其晶胞常数a＝2.86埃和c＝14.23埃。晶胞常数不是固定的常数。也就是说，晶胞常数按制备条件或添加掺杂剂如镍、钴、锌等就a而言常有从2.76到2.96埃的变化，就c而言常有从14.13到14.33的变化。活性物质对Li/Li+能显示出介于4.5V-2V的连续放电特性。
本发明的活性物质优选通过原料锰盐溶解或悬浮于锂溶液中而导致该溶液在高压和低pH溶液条件下在高压釜中反应而生成。合适的锰原料是无机盐如MnO2、Mn2O3、MnOOH、和MnCO3，有机盐如乙酸锰、丁酸锰、草酸锰、以及柠檬酸锰。合适的锂原料是LiOH、LiNO3、Li2CO3、Li2O、乙酸锂、丁酸锂、草酸锂、和柠檬酸锂。用于反应中的溶剂是净化水，和有机溶剂如乙醇、甲醇、丙酮和乙腈。反应优先在100-300℃的高温下进行。
具有层状结构的LiMnO2可由水热法合成。根据本发明高压和低温的水热法对于合成由通式AMeO2(A：Li、Na或K；Me：Mn、Ni、Co、Fe、Cr或V)表示的具有层状结构的其它物质也可使用。
实施例
参照实施例，以下详细说明本发明，但应理解不构成对本发明的限制。
在50℃下把668mg的LiOH溶解在120ml的水中，之后，把50mg的γ-MnO2浸入其中30分钟。调节溶液的pH值到1-2，再把混合物置于170℃和300大气压下的聚四氟乙烯包覆的不锈钢高压釜内加热5天，以便获得本发明的锰酸锂。
所生成的活性物质X-射线衍射图(CuK α)示于图1A中。为了比较，把具有层状结构的LiNiO2的衍射图示于图1B，通过常规固相反应(γ-MnO2和LiOH的混合物在700℃下煅烧)所得到的正交晶系LiMnO2衍射图示于图1C中。
可以看出本发明活性物质的衍射图与已知的正交晶系LiMnO2不同，而与具有层状结构的LiNiO2相同。现已确定把具有空间群为R3m的六方晶系层状结构定为衍射峰平面的指数。本发明活性物质的结构说明示于图2中。
本发明的活性物质具有两种MnO2层的堆积结构，MnO2层是由共用晶棱的MnO6八面体组成，其中锂离子由八面体配位的氧离子所包围。在该种结构中，锰离子按层状排列并由以立方密堆积排列的氧离子的八面体所包围，从而形成共用晶棱的八面体层。锂层的锂离子被夹在两层MnO6八面体之间。
现已断定本发明活性物质的结构与LiNiO2或LiCoO2的层状结构相似，其代表性的晶胞常数a＝2.86埃，c＝14.23埃。晶胞体积为101.23埃3，与LiNiO2的101.3埃3大致相同。这一点意味着具有层状结构的LiMnO2和LiNiO2易于形成固溶体。事实上，镍添加到LiMnO2中会导致晶体性能的稳定化，而且所得到的固溶体不易为充电/放电循环所损坏。
另一方面，由于正交晶系LiMnO2和LiNiO2间的结构差异，正交晶系的LiMnO2虽能形成固溶体LiMnxNi1-xO2(0≤X≤0.5)，但该固溶体的充电和放电特性按“固态离子型表面活性剂”(Solid State Ionics)，1992年第57期第311页记载是很差的。已进一步证实往本发明的活性物质中添加钴能产生相同效果。可以理解具有本发明层状结构的LiMnO2与衍射图示于图1C中的正交晶系结构的LiMnO2是有差别的。
在本例中获得的活性物质具有极好的六方晶系的层状结构，已观察到在该晶系中锰离子与锂离子之间没有置换。尽管在某些依水热反应的温度和压力而定的情况下能获得锂和锰可彼此置换的结构，但活性物质基本上还是具有层状结构的。
使用如此获得的活性物质作为正极活性物质而将金属锂作为负极制备电池。当电池在0.2C电流下充电至4.2V然后再于相同电流下放电到2V时，显示出令人满意的电化学活性。典型的放电特性曲线示于图3中。可以看出经过多次的充电/放电循环仍能保证稳定的放电特性。还可看出显示出的连续放电特性对于Li/Li+介于4.5V-2V，这样的数据到目前为止尚未报导。具有层状结构的LiMnO2已被证实是未曾发表过的廉价活性物质。LiMnO2的理论容量密度为286mAh/g。进一步优化电极的设计将会产生更高性能的电池。
尽管详细地并参照本发明的特定实施例对本发明进行了描述，但在本发明中所作的各种不偏离本发明精神和范围的变更和改进对所属技术领域的技术人员来说都是明显的。
Claims (12)
1.一种锂电池用正极活性物质包含具有六方晶系结构和空间群为R3m的锰酸锂，对Li/Li+能显示出从4.5V到2V的连续放电电压特性。
2.按权利要求1的正极活性物质，其中所述锰酸锂具有的晶胞常数a＝2.76-2.96埃和c＝14.13-14.33埃。
3.按权利要求1的正极活性物质，进一步含有镍、钴、铁、铬、锌和钒中的至少一种。
4.包含锂电池用正极活性物质的电池含有具有六方晶系结构且空间群为R3m的锰酸锂，对Li/Li+能显示从4.5V到2V的连续放电电压特性；且该锂电池还含有负极。
5.按权利要求4的电池，其中所述负极包括金属锂、碳和金属合金。
6.按权利要求4的电池，其中所述锰酸锂具有的晶胞常数a＝2.76-2.96埃和c＝14.13-14.33埃。
7.按权利要求4的电池，其中所述正极活性物质进一步含有镍、钴、锌、铁、铬和钒中的至少一种。
8.一种生产锂电池用正极活性物质的方法，其中原料锰和原料锂通过水热法起反应生成锰酸锂。
9.按权利要求8的方法，其中所述原料锰选自MnO2、Mn2O3、MnOOH、MnCO3、乙酸锰、丁酸锰、草酸锰和柠檬酸锰，所述原料锂选自LiOH、LiNO3、Li2CO3、Li2O、乙酸锂、丁酸锂、草酸锂和柠檬酸锂。
10.按权利要求8的方法，其中所述水热法是在选自净化水、乙醇、甲醇、丙酮和乙腈的溶剂中进行的。
11.按权利要求8的方法，其中所述水热法是在100℃或更高的温度下进行的。
12.按权利要求11的方法，其中所述水热法是在300℃或以下的温度下进行的。
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| KR101297385B1 (ko) * | 2012-07-09 | 2013-08-19 | 성신여자대학교 산학협력단 | 리튬 이차 전지용 양극 활물질 제조방법 |
| CN103078106B (zh) * | 2013-02-07 | 2015-05-13 | 湖南信达新材料有限公司 | 锂离子电池锰酸锂正极材料的制备方法 |
| JP6283743B2 (ja) | 2013-07-09 | 2018-02-21 | ダウ グローバル テクノロジーズ エルエルシー | カソードを形成する方法 |
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| WO2018043302A1 (ja) * | 2016-08-30 | 2018-03-08 | 国立研究開発法人産業技術総合研究所 | リチウムニッケル系複合酸化物及びその製造方法 |
| US10741839B2 (en) | 2017-03-02 | 2020-08-11 | Uchicago Argonne, Llc | Surface treatment for lithium battery electrode materials |
| CN111837265A (zh) * | 2018-03-07 | 2020-10-27 | 日立金属株式会社 | 锂离子二次电池用正极活性物质和锂离子二次电池 |
| CN109585824A (zh) * | 2018-11-23 | 2019-04-05 | 安徽工业大学 | 一种球形中空多孔锰酸锂正极材料的制备方法 |
| CN113594445A (zh) * | 2020-04-30 | 2021-11-02 | 湖南杉杉能源科技股份有限公司 | 一种多金属复合氧化物包覆改性锰酸锂正极材料及其制备方法 |
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| US5153081A (en) * | 1989-07-28 | 1992-10-06 | Csir | Lithium manganese oxide compound |
| US5316875A (en) * | 1991-07-19 | 1994-05-31 | Matsushita Electric Industrial Co., Ltd. | Secondary battery with nonaqueous electrolyte and method of manufacturing same |
| JPH05299092A (ja) * | 1992-01-17 | 1993-11-12 | Matsushita Electric Ind Co Ltd | 非水電解質リチウム二次電池及びその製造方法 |
| JP2847663B2 (ja) * | 1992-10-06 | 1999-01-20 | 日本電信電話株式会社 | 非水電解質電池 |
| US5418090A (en) * | 1993-02-17 | 1995-05-23 | Valence Technology, Inc. | Electrodes for rechargeable lithium batteries |
| CA2096264A1 (en) * | 1993-05-14 | 1994-11-15 | Jeffrey Raymond Dahn | Novel method for preparing solid solution materials for secondary non-aqueous batteries |
| JPH0710541A (ja) * | 1993-06-30 | 1995-01-13 | Tosoh Corp | リチウムマンガン複合酸化物 |
| JPH07101728A (ja) * | 1993-10-01 | 1995-04-18 | Tosoh Corp | リチウムマンガン酸化物及びその製造方法並びにその用途 |
| JPH087883A (ja) * | 1994-06-23 | 1996-01-12 | Sony Corp | 非水電解液二次電池 |
| JP3067531B2 (ja) * | 1994-07-13 | 2000-07-17 | 松下電器産業株式会社 | 非水電解液二次電池の正極活物質およびそれを用いた電池 |
-
1996
- 1996-06-13 JP JP17423296A patent/JP3846601B2/ja not_active Expired - Fee Related
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1997
- 1997-06-12 EP EP97109591A patent/EP0813256B1/en not_active Expired - Lifetime
- 1997-06-12 DE DE69712409T patent/DE69712409T2/de not_active Expired - Fee Related
- 1997-06-13 US US08/874,728 patent/US5981106A/en not_active Expired - Lifetime
- 1997-06-13 CN CN97112128A patent/CN1131571C/zh not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102299314A (zh) * | 2011-07-14 | 2011-12-28 | 上海微纳科技有限公司 | 尖晶石LiMn2O4锂离子电池正极材料的制备方法 |
| CN110615480A (zh) * | 2019-08-30 | 2019-12-27 | 浙江工业大学 | 一种动态水热法制备层状锰酸锂材料的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0813256A2 (en) | 1997-12-17 |
| US5981106A (en) | 1999-11-09 |
| JP3846601B2 (ja) | 2006-11-15 |
| CN1131571C (zh) | 2003-12-17 |
| DE69712409T2 (de) | 2003-04-03 |
| EP0813256B1 (en) | 2002-05-08 |
| JPH103921A (ja) | 1998-01-06 |
| EP0813256A3 (en) | 1998-09-16 |
| DE69712409D1 (de) | 2002-06-13 |
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