CN1151072C - 生产尖晶石型锰酸锂的方法、阴极材料和非水电解质二次电池 - Google Patents
生产尖晶石型锰酸锂的方法、阴极材料和非水电解质二次电池 Download PDFInfo
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 46
- 239000011029 spinel Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 37
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 4
- 238000010298 pulverizing process Methods 0.000 claims abstract description 3
- 239000010406 cathode material Substances 0.000 claims description 27
- 239000007858 starting material Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 18
- 229910052708 sodium Inorganic materials 0.000 description 18
- 239000011734 sodium Substances 0.000 description 18
- 238000003860 storage Methods 0.000 description 17
- 239000011572 manganese Substances 0.000 description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 12
- 238000006386 neutralization reaction Methods 0.000 description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910015645 LiMn Inorganic materials 0.000 description 3
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241001504664 Crossocheilus latius Species 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 210000001503 joint Anatomy 0.000 description 1
- 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 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002663 nebulization Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- C01P2002/00—Crystal-structural characteristics
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- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
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- C01P2004/60—Particles characterised by their size
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract
本发明提供一种生产尖晶石型锰酸锂的方法,其特征在于,包括下列步骤:粉碎电沉积的二氧化锰、将该粉末用氢氧化钠或碳酸钠中和至pH值为2至6.0、将电解二氧化锰与锂的原始材料混合并将该混合物在600~1000℃的温度下焙烧。本发明还提供一种用于非水电解质二次电池的阴极材料,其中含有通过上述的生产方法获得的尖晶石型锰酸锂。本发明也提供一种非水电解质二次电池,其由使用了上述的阴极材料的阴极、能吸收和脱除锂的阳极以及无水电解液所构成。
Description
技术领域
本发明涉及的是一种生产尖晶石型锰酸锂的方法。更确切地说是一种生产用作非水电解质二次电池的阴极材料的尖晶石型锰酸锂的方法,这种尖晶石型锰酸锂能抑制锰从中的溶解,从而可靠地改善电池的高温特性如高温蓄电性能和高温循环特性。本发明还涉及一种非水电解质二次电池,其含有使用了上述的阴极材料的阴极。
背景技术
随着近年来手提电子设备和无线电子器材如个人电脑和电话的迅速发展,对作为驱动电源的二次电池的需求正在增加。特别希望非水电解质二次电池具有最小的尺寸而有高的能量密度。能满足作为非水电解质二次电池的阴极活性物质要求的有钴酸锂(LiCoO2)、镍酸锂(LiNiO2)、锰酸锂(LiMn2O4)等等。由于这些复合氧化物相对锂具有4V或更高的电极电位,因此它们能给电池提供高的能量密度。
在上面所说的复合氧化物中,LiCoO2和LiNiO2所具有的理论容量约为280mAh/g,而LiMn2O4所具有的理论容量低达148mAh/g,但它被认为适合用于电子设备等,这是因为作为原始材料的氧化锰来源丰富而廉价,并且它还避免了对LiNiO2所观测到的在充电时的热不稳定性。
但是锰酸锂(LiMn2O4)的缺点在于在高温下锰会从中溶解出,从而降低电池高温性能,如高温蓄电性能和高温循环特性。
发明内容
因此,本发明的目的是要提供一种生产用作非水电解质二次电池的阴极材料的尖晶石型锰酸锂的方法,这种尖晶石型锰酸锂能抑制锰从中的溶解,从而可靠地改善电池的高温特性诸如高温蓄电性能和高温循环特性,以及提供使用了这种阴极材料的二次电池。
日本专利公开No.139861/90指出,将给定数量的钠加入到尖晶石型锰酸锂中,从而改善其室温循环寿命。该公开文献所说的方法是将钠的原始材料加入到锰的原始材料和锂的原始材料中,并且将混合物烧结。由于电解二氧化锰廉价而丰富,它适合作为尖晶石型锰酸锂的锰的原始材料。电解以后,电解二氧化锰通常与氨中和用于锰干电池和与苏打中和用于碱性锰电池。人们知道苏打中和的电解二氧化锰中含有少量的残留钠。残留钠的数量依赖于中和条件。
本发明人注意到了电解二氧化锰的中和条件,并发现在特殊的中和条件下获得的尖晶石型锰酸锂能够达到上述目的。
基于以上的发现本发明的目的已被实现,并提供一种生产尖晶石型锰酸锂的方法,其特征在于,包括下列步骤:粉碎电沉积的二氧化锰、将该粉末用氢氧化钠或碳酸钠中和至pH值为2至6.0、将电解二氧化锰与锂的原始材料混合并将该混合物在600~1000℃的温度下焙烧。
本发明还提供一种用于非水电解质二次电池的阴极材料,其中含有通过上述的生产方法获得的尖晶石型锰酸锂。
本发明也提供一种非水电解质二次电池,其由使用了上述的阴极材料的阴极、能吸收和脱除锂的阳极以及无水电解液所构成。
附图说明
图1是在实施例和比较实施例中制备的币式非水电解质二次电池的横截面示意图。
具体实施方式
现在详细叙述本发明。
在本发明中,电解二氧化锰是用作尖晶石型锰酸锂中锰的原始材料。
用于本发明的电解二氧化锰是通过下面方法获得的。例如,在加热的同时以恒定的电流密度,通过用碳片为阴极,钛片为阳极来电解有指定浓度的硫酸锰溶液,使二氧化锰在阳极电沉积。将电沉积的二氧化锰从阳极上剥下并粉碎至指定的粒度,优选平均粒径为5~30μm。
由于非水电解质二次电池的阴极有一约100μm厚的薄膜形状,因此太大的颗粒将引起薄膜的开裂等类似问题,并难以形成厚度均匀的薄膜。从平均粒径为5~30μm的电解二氧化锰合成制得的尖晶石型锰酸锂用作阴极材料不必进一步粉碎操作就适合薄膜的形成。建议将这样获得的细粒化的电解二氧化锰用钠中和,在这一过程中使钠能均匀分布。
在经苏打中和以后,将粉碎至指定粒度的电解二氧化锰用水冲洗并干燥。特别指出,苏打中和是用氢氧化钠或碳酸钠来实现的。粉碎和中和的顺序没有特别地限制。也就是说,中和也可以先于粉碎。
中和电解二氧化锰的pH值为2或更高,优选2~5.5,更优选2~4。pH值越高,在高温下锰的溶解量就越少,但是初始放电容量也就越少。pH值低于2则效果不足。
在本发明中,将所得的电解二氧化锰与锂的原始材料混合并焙烧制得尖晶石型锰酸锂。锂盐包括碳酸锂(Li2CO3)、硝酸锂(LiNO3)和氢氧化锂(LiOH)。锂原始材料中的锂与电解二氧化锰中的锰之摩尔比(Li/Mn)优选为0.50~0.60。
为了获得更大的反应横截面积,在混合之前或之后优选将电解二氧化锰和锂原始材料粉碎。称重和混合材料可以这样进行,也可以在粒状化以后进行。粒状化可以在湿状态下进行,也可以在干燥状态下进行。粒状化的方法包括活塞粒状化、碾转粒状化、流态化床粒状化、混合粒状化、干雾化、压力成形(pressure forming)粒状化以及轧制薄片粒状化,等等。
将所得的原始材料放入焙烧炉中在600~1000℃焙烧而获得尖晶石型锰酸锂。虽然焙烧温度在600℃左右足以获得单相的尖晶石型锰酸锂,但是在低焙烧温度下晶粒并没有长大。因此焙烧温度需要在750℃或更高,优选850℃或更高。可以使用的焙烧炉包括砖窑和定式炉。焙烧时间为1小时或更长,优选5~20小时。
通过这种方法可以获得具有给定含量钠的尖晶石型锰酸锂。优选钠含量为0.05~1.0%重量。含钠的尖晶石型锰酸锂被用作非水电解质二次电池的阴极材料。
在本发明的非水电解质二次电池中,上述所说的阴极材料是将导电物质如碳黑和如聚四氟乙烯的粘结剂混合而制备的阴极材料混合物。用作阳极是锂或能吸收和脱除锂的物质如碳。可以使用的无水电解液没有特别的限制,包括锂盐如六氟磷酸锂(LiPF6)溶入混合溶剂(如碳酸乙烯酯/碳酸二甲酯)中。
由于锰在充电状态能被抑制溶解,因此根据本发明的非水电解质二次电池表现改善的电池高温特性如高温蓄电性能和高温循环特性。
现在将参照实施例更加详细地叙述本发明,但是必须知道本发明并不受此限制。
实施例1
制备含有硫酸浓度为50g/L和锰浓度为40g/L的硫酸锰水溶液作为电解液。电解液被加热至95℃,同时用碳片作为阴极钛片作为阳极,以60A/m2的电流密度对其进行电解。将这样电沉积制得的二氧化锰剥下并撞碎成7mm的碎片,再将其粉碎成平均粒度约为20μm。
用20L的水来冲洗10公斤的二氧化锰。将冲洗水放出后,再将20L的水中加入该二氧化锰中,把35g的氢氧化钠溶解在里面,随后搅拌24小时并完成中和。颗粒用水冲洗、过滤并干燥(50℃×30mins.)。pH值的测试根据JIS K1467-1984进行,所得粉末中钠的含量示于表1。
将这样获得的具有平均粒度约为20μm的1Kg的二氧化锰与碳酸锂以Li/Mn摩尔比为0.54进行混合,将混合物放入箱式炉中在800℃下焙烧20小时。
将80份重量的所得的尖晶石型锰酸锂、15份重量的碳黑与5份重量的聚四氟乙烯(粘结剂)混合制得阴极材料混合物。
通过使用所得的阴极材料混合物组装的币式非水电解质二次电池示于图1。阴极壳体1是由耐有机电解液的不锈钢制成,在其的内表面侧点焊着同样不锈钢的集流器3。在集流器3的上面压结着由阴极材料混合物制成的阴极。浸渍着电解液的多孔的聚丙烯树脂隔膜6被放置在阴极5的上表面。密封件2(其下面粘结着由金属锂制成的阳极4)嵌入阴极壳体1的开口并经过聚丙烯垫圈7将电池密封。密封件2兼有作为阳极端接头的作用,它是由与阴极壳体1类似的不锈钢制成的。电池的直径为20mm高为1.6mm。所用的电解液由等体积混合的碳酸乙二酯和1,3-二甲氧基乙烷所组成,并溶入有1摩尔/升的六氟磷酸锂作为溶质。
将所得的电池进行充放电试验,充放电试验是在20℃、电流密度为0.5mA/cm2、电压为3V~4.3V下进行的。将电池充电至4.3V并将其在80℃下放置3天后以确定电池的放电容量。另外,电池的蓄电特性以蓄电以后的放电容量的滞留量来确定,即以蓄电以前的放电容量为100。这样获得的初始放电容量和高温蓄电滞留量示于表1。
实施例2
除了将中和电解二氧化锰的氢氧化钠的量替换为53g外,用实施例1的同样方法合成制得尖晶石型锰酸锂。中和以后pH值和钠的含量示于表1。使用所获得的尖晶石型锰酸锂作为阴极材料组装成币式非水电解质二次电池,用实施例1的同样方法测得电池的初始放电容量和高温蓄电滞留量。所得结果示于表1。
实施例3
除了将中和电解二氧化锰的氢氧化钠的量替换为80g外,用实施例1的同样方法合成制得尖晶石型锰酸锂。中和以后pH值和钠的含量示于表1。使用所获得的尖晶石型锰酸锂作为阴极材料组装成币式非水电解质二次电池,用实施例1的同样方法测得电池的初始放电容量和高温蓄电滞留量。所得结果示于表1。
实施例4
除了将中和电解二氧化锰的氢氧化钠的量替换为120g外,用实施例1的同样方法合成制得尖晶石型锰酸锂。中和以后pH值和钠的含量示于表1。使用所获得的尖晶石型锰酸锂作为阴极材料组装成币式非水电解质二次电池,用实施例1的同样方法测得电池的初始放电容量和高温蓄电滞留量。所得结果示于表1。
实施例5
除了将中和电解二氧化锰的氢氧化钠的量替换为160g外,用实施例1的同样方法合成制得尖晶石型锰酸锂。中和以后pH值和钠的含量示于表1。使用所获得的尖晶石型锰酸锂作为阴极材料组装成币式非水电解质二次电池,用实施例1的同样方法测得电池的初始放电容量和高温蓄电滞留量。所得结果示于表1。
实施例6
除了将焙烧温度替换为900℃外,用实施例1的同样方法合成制得尖晶石型锰酸锂。中和以后pH值和钠的含量示于表1。使用所获得的尖晶石型锰酸锂作为阴极材料组装成币式非水电解质二次电池,用实施例1的同样方法测得电池的初始放电容量和高温蓄电滞留量。所得结果示于表1。
实施例7
除了将焙烧温度替换为700℃外,用实施例1的同样方法合成制得尖晶石型锰酸锂。中和以后pH值和钠的含量示于表1。使用所获得的尖晶石型锰酸锂作为阴极材料组装成币式非水电解质二次电池,用实施例1的同样方法测得电池的初始放电容量和高温蓄电滞留量。所得结果示于表1。
比较实施例1
除了没有进行中和电解二氧化锰的步骤外(即氢氧化钠的加入量为0g),用实施例1的同样方法合成制得尖晶石型锰酸锂。中和以后pH值和钠的含量示于表1。使用所获得的尖晶石型锰酸锂作为阴极材料组装成币式非水电解质二次电池,用实施例1的同样方法测得电池的初始放电容量和高温蓄电滞留量。所得结果示于表1。
表1
pH值(JIS) | 钠(重量%) | 初始放电容量(mAh/g) | 高温蓄电滞留量(%) | ||
实施例 | 1 | 2.5 | 0.13 | 122 | 75 |
2 | 3.5 | 0.20 | 118 | 79 | |
3 | 4.5 | 0.45 | 114 | 82 | |
4 | 5.0 | 0.54 | 113 | 85 | |
5 | 6.0 | 0.65 | 107 | 86 | |
6 | 3.5 | 0.20 | 116 | 88 | |
7 | 3.5 | 0.20 | 119 | 70 | |
比较实施例1 | 1.6 | 0.04 | 123 | 64 |
实施例8
除了将电解二氧化锰粉碎至平均粒度为5μm外,用实施例1的同样方法合成制得尖晶石型锰酸锂。用实施例1的同样方法,将所获得的尖晶石型锰酸锂作为阴极材料组装成币式非水电解质二次电池。充放电试验在电流密度为0.5mA/cm2和1.0mA/cm2下进行。在电流密度为1.0mA/cm2的放电容量与在电流密度为0.5mA/cm2(作为100)的放电容量之比作为负载电流比率。负载电流比率示于表2。
实施例9
在实施例1中制备的币式非水电解质二次电池以实施例8的同样方法对其进行测试。负载电流比率示于表2。
实施例10
除了将电解二氧化锰粉碎至平均粒度为30μm外,用实施例1的同样方法合成制得尖晶石型锰酸锂。用实施例1的同样方法,将所获得的尖晶石型锰酸锂作为阴极材料组装成币式非水电解质二次电池,用实施例8的同样方法对其进行测试。负载电流比率示于表2。
实施例11
除了将电解二氧化锰粉碎至平均粒度为35μm外,用实施例1的同样方法合成制得尖晶石型锰酸锂。用实施例1的同样方法,将所获得的尖晶石型锰酸锂作为阴极材料组装成币式非水电解质二次电池,用实施例8的同样方法对其进行测试。负载电流比率示于表2。
表2
平均粒度(μm) | 负载电流比率(%) | ||
实施例 | 8 | 5 | 92 |
9 | 20 | 89 | |
10 | 30 | 84 | |
11 | 35 | 71 |
正如上面所述,用本发明的方法获得的尖晶石型锰酸锂作为非水电解质二次电池的阴极材料,使其可能在充电时抑制锰的溶解从而改善电池的特性,如电池的高温蓄电性和高温循环特性以及负载电流比率。
Claims (5)
1.一种生产尖晶石型锰酸锂的方法,其特征在于,包括下列步骤:粉碎电沉积的二氧化锰、将该粉末用氢氧化钠或碳酸钠中和至pH值为2至6.0、将电解二氧化锰与锂的原始材料混合并将该混合物在600~1000℃的温度下焙烧。
2.如权利要求1所述的生产尖晶石型锰酸锂的方法,其中,粉碎的二氧化锰具有的平均粒度为5~30μm。
3.如权利要求1或2所述的生产尖晶石型锰酸锂的方法,其中,焙烧是在750~1000℃的温度下进行的。
4.一种用于非水电解质二次电池的阴极材料,其中含有通过权利要求1,2或3所述的生产方法获得的尖晶石型锰酸锂。
5.一种非水电解质二次电池,其由使用了权利要求4所述的阴极材料的阴极、能吸收和脱除锂的阳极以及无水电解液所构成。
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JP2001236957A (ja) | 2000-02-25 | 2001-08-31 | Mitsui Mining & Smelting Co Ltd | リチウム一次電池用二酸化マンガン及びその製造方法 |
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US20050164085A1 (en) * | 2004-01-22 | 2005-07-28 | Bofinger Todd E. | Cathode material for lithium battery |
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US8298701B2 (en) | 2011-03-09 | 2012-10-30 | Aquion Energy Inc. | Aqueous electrolyte energy storage device |
US8945751B2 (en) | 2011-07-19 | 2015-02-03 | Aquion Energy, Inc. | High voltage battery composed of anode limited electrochemical cells |
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US8945756B2 (en) | 2012-12-12 | 2015-02-03 | Aquion Energy Inc. | Composite anode structure for aqueous electrolyte energy storage and device containing same |
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