CN1098270C - 氟磷酸锂和其作为导电盐的用途 - Google Patents
氟磷酸锂和其作为导电盐的用途 Download PDFInfo
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- 150000003839 salts Chemical class 0.000 title claims description 30
- SXWUDUINABFBMK-UHFFFAOYSA-L dilithium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical class [Li+].[Li+].[O-]P([O-])(F)=O SXWUDUINABFBMK-UHFFFAOYSA-L 0.000 title abstract 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 37
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Abstract
本发明涉及通式(I)的新型氟磷酸锂Li+[PFa(CHbFc(CF3)d)e]- (I)其中:a为1,2,3,4或5,b为0或1,c为0,1,2或3,d为0,1,2或3和e为1,2,3或4,条件是a+e的总数等于6,b+c+d的总数等于3且b和c不同时为0,其条件是配位体(CHbFc(CF3)d)可以不同,涉及所述化合物的制备方法、它们作为电解质的用途和使用所述电解质制备的锂电池。
Description
本发明涉及通式(I)的新型氟磷酸锂、所述化合物的制备方法、它们在电解质中的用途,和用所述电解质生产的锂电池
Li+[PFa(CHbFc(CF3)d)e]- (I)其中:a为1,2,3,4或5,b为0或1,c为0,1,2或3,d为0,1,2或3和e为1,2,3或4,条件是a+e的总数等于6,b+c+d的总数等于3且b和c不同时为0,其条件是配位体(CHbFc(CF3)d)可以不同。
本发明还涉及用于生产通式(I)化合物所需的、作为中间产物的通式(Ia)的化合物
[PFa(CHbFc(CF3)d)e] (Ia)其中:如通式(I),b为0或1,c为0,1,2或3,d为0,1,2或3和e为1,2,3或4,但是a为1,2,3或4。
通常,人们将六氟磷酸锂用作锂蓄电池中的导电盐。缺点是该盐的耐水解性较差。因此,人们进行了各种试验,发现了所述盐的代用品。例如WO 88/03331公开了环状全氟链烷双(磺酰基)酰亚胺的盐,也包括它们的锂盐,它可用作锂蓄电池中的非水电解质中的导电盐。但是,正如试验所揭示的,只能高成本地来生产这类化合物,并且在合成后,必须除去不希望有的副产物。盐的纯化是不可缺少的,原因是再现性是作为电池电解质的成分使用时不可缺少的参数。
因此,本发明的目的是,提供合适的用作锂电池中电解质的导电盐。本发明的目的还是提供制备方法,以容易和廉价地生产按照本发明的导电盐。
本发明的目的通过通式(I)的新型氟磷酸锂来实现
Li+[PFa(CHbFc(CF3)d)e]- (I)其中:a为1,2,3,4或5,b为0或1,c为0,1,2或3,d为0,1,2或3和e为1,2,3或4,条件是a+e的总数等于6,b+c+d的总数等于3且b和c不同时为0,其条件是配位体(CHbFc(CF3)d)可以不同,所述的氟磷酸锂可以代替传统的用作锂蓄电池中的导电盐的六氟磷酸锂,它们还可以与六氟磷酸锂的混合物形式使用。
因此,本发明涉及本发明通式(I)的新型盐,还涉及它们的制备方法和通式(Ia)的化合物,
[PFa(CHbFc(CF3)d)e] (Ia)其中:如通式(I),b为0或1,c为0,1,2或3,d为0,1,2或3和e为1,2,3或4,但是a为1,2,3或4,该式(Ia)的化合物是作为生产通式(I)的盐所需的中间产物。
最后,本发明还涉及含有本发明盐的电解质和采用所述电解质生产的电化学电池。这类电化学电池可以是原电池或蓄电池,它们含有通式(I)的锂化合物。
为了生产本发明的盐,首先,将合适的二氯单-、氯二烷基膦、二氟单-、氟二烷基亚膦(hosphanes)、氯二氟-、二氯氟-、三氟二烷基正膦或四氯氟烷基正膦、氯-或氟烷基次膦酸酐或二氯-或二氟烷基膦酸酐、氯-或氟二烷基膦氧化物或三烷基膦氧化物溶解在溶剂中,并按已知方法、在-15-20℃的温度和常压下进行电化学氟化。用于该反应的合适溶剂是氟化氢。当已经消耗掉理论电量的90-150%、尤其是110-130%时结束氟化反应。该值由库仑测定法确定。
本发明通式(I)的实用盐通过如下方式制备,将第一阶段获得的氟化烷基正膦优选在蒸馏分离后、在无水条件下,作为产物混合物溶解在合适的非质子传递溶剂,极性溶剂,例如二甲醚、二甲氧基乙烷或它们的混合物中,并根据反应性,在0-60℃的温度,优选室温下与氟化锂反应,形成通式(I)的化合物。
在本发明的电解质中,可使用通过氟化反应获得的通式(I)的纯化合物和混合物。优选地,因电解质特性的再现性,用纯化合物来生产电解质溶液。
通过试验,令人惊奇地发现,通式(I)的化合物在非质子传递溶剂中,在室温下耐水解并且,具体地说,尤其是烷基完全被氟饱和的那些化合物。在这方面,耐水解性随着分子中氟原子数而增加。
非质子传递溶剂是指这样的一些溶剂,例如--腈 乙腈或苄腈,--醚 二***、二甲氧基乙烷、四氢呋喃、二噁烷或二甲基四
氢呋喃,--酯 甲酸、乙酸、丙酸的甲酯或一乙酯,以及环酯,例如丁内酯,
和有机碳酸酯,例如碳酸二甲酯、碳酸二乙酯、碳酸乙甲
酯、碳酸乙烯酯或碳酸丙烯酯,--酰胺 二甲基甲酰胺、二乙基甲酰胺、N-甲基吡咯烷,或--砜 二甲基砜、四亚甲基砜或其它环丁砜。
另外,本发明的盐在所述的溶剂中具有极好的溶解性,尤其是完全被氟饱和的化合物几乎不吸湿。
试验已经表明,这些化合物极其稳定。在以固态干燥贮存时,全氟化的化合物在低于100℃的温度下不分解。试验证明,甚至在进一步升高的温度下,它们都极其稳定。仅在高于130℃的温度下,它们才略微脱色。
甚至将它们在贮存在溶液中、例如二甲氧基乙烷中时,都未观察到颜色变化,即使在数周后,都未检测到分解产物。
为此,本发明的化合物,尤其是通式III、IV、V、VI和VII的化合物已经极适合于作为锂电池的非水电解质中的导电盐。
此外,含有这些化合物的电解质溶液具有明显的化学和电化学稳定性。尤其是,在锂沉积之前,不能检测到对应阴离子的氧化。
这类电解质除了有机锂盐,例如本发明通式(I)的化合物外,还包括一种或多种非水有机溶剂,任选地包括其它添加剂。必要时,除了本发明的化合物外,也可将已经已知的锂盐加入到电解质中,以用作导电盐。对这类电解质和锂电池的结构或操作模型的进一步详细描述对于本技术领域的熟练技术人员来说是已知的。本发明化合物的使用与该领域中已知锂化合物完全类似,并且在这些条件下,显示出极高的稳定性。对应的电池组电池在电容量和恒压方面具有极好的特性,并且在大量的充电-放电循环中,其使用性能也不受限制。
下面给出的实施例更详细地描述了本发明,但目的不是对本文公开的本发明特征进行限制。
实施例1双(七氟异丙基)三氟正膦(IIa)和其衍生物
二异丙基氯亚膦是通过Simons法,在含有溶剂氟化氢的电化学电解池中电化学氟化的。所使用的体积为310cm3的圆柱形电解池配备有镍阳极,和阴极,镍阳极的有效表面积S=3.75dm2,阴极具有相同的有效表面积。此外,电解池配备有冷却冷凝器。在电解期间,使电解池的温度保持在-5℃,冷凝器保持在-30℃。
将57g溶解在200g氢氟酸中的二异丙基氯膦分批加入到235g预先电解的氢氟酸中,具体地说,按以下方式进行:电解时间 二异丙基氯亚膦的用量[g][A小时]0 1078.1 10157.4 10230.6 10294.0 10365.2 7
已经通过了冷却冷凝器和两个PTFE收集器的气态产物被冷却到-78℃。
在电流消耗值为420A小时(理论值的131%)后,中止在电压为4.4-5.4V和电流密度为0.30-0.53A/dm2下进行的电解,从电解池中收集到约220g液态产物。在将温度调节到-20℃并从氟化氢相中分离出下层相(lower phase)后,获得18g粗产物。通过NMR 19F分光镜,可检测到75%双(七氟异丙基)三氟正膦(IIa),15%七氟异丙基(1,1,1,3,3,3-六氟异丙基)三氟正膦(IIb)和双(六-1,1,1,3,3,3-六氟异丙基)三氟正膦(IIc)。
通过分馏,可将该混合物分离成分馏物,它们各含有作为主要组分的这些化合物中的一种。另外,在分离出氟化氢相后,从冷却收集器中获得33g在低温下呈液态的产物。NMR 19F分光镜探测表明,它们主要是七氟异丙基四氟正膦(IId)、1,1,13,3,3-六氟异丙基四氟正膦(IIe)和全氟丙烷。在加热到20℃时可蒸馏掉全氟丙烷。残余物可通过分馏分离成主要成分为七氟异丙基四氟正膦(IId)或1,1,1,3,3,3-六氟异丙基四氟正膦(IIe)的分馏物。
-39.72dtm(3F1)
-70.15m(12F3)
-171.78dm(2F2)J3 F 1 F 2=8.0HzNMR 31P,ppm:
-26.0qtm
J1 P,F 1=1083Hz
J2 P,F 2=102Hz
-33.10dm(3F1)
-59.56m(6F4)
-70.26m(6F3)
-171.90m(1F2)NMR 31P,ppm:
-23.2qdm
J1 P,F 1=1014.0Hz
J2 P,F 2=99.0Hz
J3 P,F 3=5.2Hz
J3 P,F 4=5.7Hz
J2 P,H=11.0HzNMR 1H,ppm:
3.9dm双(六-1,1,1,3,3,3-六氟异丙基)三氟正膦(IIc):NMR 19F,ppm:
-25.96dm(3F1)
-59.51m(12F2)NMR 31P,ppm:
J1 P,F 1=960.0Hz
J3 P,F 2=11.3HzNMR 1H,ppm:
3.9dm七氟异丙基四氟正膦(IId):NMR 19F,ppm:(CD3CN膜;-30℃)
-50.10dm(4F1)
-72.22m(6F3)
-172.83dm(1F2)NMR 31P,ppm:(CD3COCD3膜;-40℃);
-55.3pdsep
J1 P,F 1=1042.0Hz
J2 P,F 2=100.0Hz
-40.90dm(4F1)
-61.8m(6F2)NMR 31P,ppm:(CD3COCD3,膜);-40℃);
-50.8pdsep
J1 P,F 1=1003.0Hz
J3 P,F 2=14.0Hz
J2 P,H=27.0Hz
实施例2三(五氟乙基)二氟正膦(Va)
与实施例1描述的方法类似,用69g氧化三乙基膦制备70g三(五氟乙基)二氟正膦(Va)。NMR 31P分光镜数据与文献(V.J.Semenii等人;Zh.Obshch.Khim.(俄罗斯)1985,第55卷,12,2716-2720)中的一致:NMR 31P,(具有85%H3PO4的CD3COCD3膜作为内标),ppm:
-47.55tsep
J1 P,F=1003.0Hz
J2 P,F=122.0Hz实施例3双(七氟异丙基)四氟磷酸锂(II)
在用磁性搅拌器搅拌、排湿的同时,将12g(0.028摩尔)双(七氟异丙基)三氟正膦(IIa)缓慢地加入到装在PTFE反应器的溶液中,所述溶液由0.82g(0.031摩尔)LiF和60ml预干燥的二甲氧基乙烷组成,通过冰水浴冷却,使反应温度保持在室温。然后,在相同的温度下,搅拌1小时,再加入少量的金属锂。使反应混合物在室温下保持24小时,然后进行过滤,并将它们立即用作再充电式电池的电解质。但是,也可通过高真空蒸馏,蒸馏掉溶剂,离析出反应期间形成的双(七氟异丙基)四氟磷酸锂(II)。
离析出锂配合物盐(II),Li+[(i-C3F7)2PF4]-×2DME,熔点:126-128℃;高达130℃时是热稳定的。分析:Li
理论值: 0.93%
实际值: 1.15%
可通过在高真空、80℃的温度下,加热配合物盐(II)几天,可除去结晶水。
实施例3a
为了制备本发明的锂盐,无需预先的分馏,可直接使用实施例1中获得的氟代正膦混合物。
如上所述,将16g实施例1的含75%化合物(IIa),15%化合物(IIb)和10%化合物(IIc)的氟代正膦混合物加入到由1.0g LiF和80ml干燥的DME组成的溶液中。也将该溶液在过滤后直接用作电解质。但是,如果向DME溶液中加入预干燥的己烷,那么也可结晶出溶液中的Li盐。通过用由干燥的DME和二丁基醚(1∶2)组成的溶剂混合物再结晶获得的产物,可与6%七氟异丙基(1,1,1,3,3,3-六氟异丙基)四氟磷酸锂(III)一起获得13.6g双(七氟异丙基)四氟磷酸锂(II)。
通过NMR19F和31P分光镜检测盐(II)和(III)的结构。用CCl3F测定CD3COCD3溶液中的NMR光谱,或者用85%H3PO4作为外标。双(七氟异丙基)四氟磷酸锂(II)NMR 19F,ppm:-58.14dm(4F1)
-71.07pdd(12F3)
-184.40dpsep(2F2)
J3 F 1 ,F 2=4.0Hz
J4 F 1 ,F 3=10.9Hz
J3 F 2 ,F 3=4.7HzNMR 31P,ppm:-149.27ptm
-148.42ptm(CD3CN溶液)
J1 P,F 1=943.0Hz
J2 P,F 2=75.0Hz
J3 P,F 3=8.2Hz七氟异丙基(1,1,1,3,3,3-六氟异丙基)四氟磷酸锂(IV)NMR 19F,ppm:-47.20dddm(4F1)
-58.01dpd(6F4)
-70.79pdd(6F3)
-183.50dm(1F2)
J3 F 1 ,F 2=4.1Hz
J3 H,F 1=4.1Hz
J3 F 2 ,F 3=8.0Hz
J4 F 1 ,F 3=11.5Hz
J4 F 1 ,F 4=11.5HzNMR 31P,ppm:-147.37pdm
J1 P,F 1=928.0Hz
J2 P,F 2=74.5Hz
J3 P,F 3=8.3Hz
J3 P,F 4=11.4Hz
实施例4七氟异丙基五氟磷酸锂(VIII)
类似于上述实施例3的方式,通过使氟代正膦(IId)与干燥二甲氧基乙烷中的LiF反应,获得七氟异丙基五氟磷酸锂(VIII)。如上所述,将过滤后获得的溶液直接用作电解质溶液,或通过高真空蒸馏,蒸馏掉溶剂或由加入的己烷引起结晶,离析出上述的盐。
也可无需预先进行提纯,通过使按实施例1获得的氟正膦的混合物与LiF反应来制备电解质溶液。还可将在这种情况下获得的两种锂盐(VIII)和(IX)溶液用作锂电池的电解质。
可按如上所述的相同方式离析出两种盐。七氟异丙基五氟磷酸锂(VIII)NMR 19F,ppm:(溶剂:CD3COCD3;标准:CCl3F)
-62.62dddsep(4F1)
-73.13p(1F2)
-71.49pdd(6F4)
-183.72dpsepm(1F3)
J2 F 1 ,F 2=45.4Hz
J3 F 1 ,F 3=3.6Hz
J3 F 3 ,F 4=4.2Hz
J4 F 1 ,F 4=11.4HzNMR 31P,ppm:(溶剂:CD3CN;外标:85%H3PO4)
-148.16pddsepJ1 P,F 1=841.0Hz
J1 P,F 2=717.0Hz
J2 P,F 3=68.7Hz
J3 P,F 4=4.9Hz1,1,1,3,3,3-六氟异丙基五氟膦酸锂(IX)NMR 19F,ppm:(溶剂:CD3COCD3;标准:CCl3F)
-52.95dddsep(4F1)
-69.04p(1F2)
-59.40dp(6F3)
J2 F 1 ,F 2=42.6Hz
J3 F 1 ,H=3.8Hz
J4 F 1 ,F 3=12.3HNMR 31P,ppm:(溶剂:CD3CN;外标:85%H3PO4)
-145.82pddsep
J1 P,F 1=829.0Hz
J1 P,F 2=708.0Hz
J2 P,H=29.0Hz
J3 P,F 3=12.9Hz
使用溶于DEM中并加入19ml LP10(其中LP10为如下组成的电解液:1M LiPF6,EC∶DMC∶PC=1∶3∶1(重量%))的1ml七氟丙基五氟磷酸锂(VIII)进行环化试验,第1个和第5个环化试验的结果列于图1中。该试验是在下列条件下进行的:电势间隔: 0.0-3.0V(结果见图1a);3.0-6.0V(结果见图1b)改变的速率: 100mV/s工作电极: Pt,表面积1.96×103cm2参考电极: Li实验电极: Li电化学稳定性:高达5.0V
实施例5三(五氟乙基)三氟磷酸锂(V)
类似于实施例3,通过使类似于实施例2获得的对应氟代正膦(Va)与预干燥的二甲氧基乙烷中的LiF反应,获得三(五氟乙基)三氟磷酸锂(V)。在这种情况下,也可将反应和过滤后获得的反应溶液直接用作电解质,或通过高真空蒸馏,蒸馏掉溶剂或由加入的己烷引起结晶,离析出盐(V)。三(五氟乙基)三氟磷酸锂(V)NMR 19F,ppm:(溶剂:CD3COCD3;标准:CCl3F)
-87.0d(2F1)
-43.6dm(1F2)
-115.3m(4F3)
-115.7m(2F5)
-79.7m(3F6)
-81.3m(6F4)NMR 31P,ppm:(溶剂:CD3CN;标准:85%H3PO4)
-149.8tdpt
J1 P,F 1=902.0Hz
J1 P,F 2=889.0Hz
J2 P,F 3=98.0Hz
J2 P,F 5=83.0Hz
三(五氟乙基)三氟磷酸锂(V)具有的熔点为116-118℃,高达130℃时是热稳定的。
图2:使用1ml溶解在DME(加入了19ml LP10,其中LP10为如下组成的电解液:1MLiPF6,EC∶DMC∶PC=1∶3∶1(重量%))中的三(五氟乙基)三氟磷酸锂(V)进行环化试验。第一次和第五次环化试验的结果示于图2中。这些试验是在下列条件下进行的:电势间隔: 0.0-3.0V(结果见图2a);3.0-6.0V(结果见图2b)改变的速率: 100mV/s工作电极: Pt,表面积1.96×103cm2参考电极: Li实验电极: Li电化学稳定性:高达5.0V
Claims (10)
1.通式(I)所示的氟磷酸锂的制备方法
Li+[PFa(CHbFc(CF3)d)e]- (I)其中:a为1,2,3,4或5,b为0或1,c为0,1,2或3,d为0,1,2或3和e为1,2,3或4,条件是a+e的总数等于6,b+c+d的总数等于3且b和c不同时为0,其条件是配位体(CHbFc(CF3)d)可以不同,其特征在于:a)将氯一-、氯二-、氯三-或氯四烷基亚膦在一种惰性溶剂中电化学氟化,b)可以通过蒸馏,使获得的产物混合物分离成不同的氟化产物和c)在非质子传递溶剂、极性溶剂中,在-35至60℃的温度下,使氟化的烷基亚膦与氟化锂进行反应。
2.根据权利要求1的方法,其特征在于:氟化是在-20℃至室温和常压下进行的。
3.根据权利要求1的方法,其特征在于:氟化产物的蒸馏提纯是在惰性气体气氛中进行的。
4.根据权利要求1的方法,其特征在于:与氟化锂的反应是在室温下进行的。
5.通式(Ia)的化合物作为制备根据权利要求1的通式(I)的化合物的中间体的用途,
[PFa(CHbFc(CF3)d)e] (Ia)其中:a为1,2,3或4b为0或1,c为0,1,2或3,d为0,1,2或3和e为1,2,3或4,条件是:a+e之和为5,b+c+d之和为3,并且b和c不同时为0,且试剂(CHbFc(CF3)d)可以不同。
6.通式(I)的氟磷酸锂
Li+[PFa(CHbFc(CF3)d)e]- (I)其中:a为1,2,3,4或5,b为0或1,c为0,1,2或3,d为0,1,2或3和e为1,2,3或4,条件是,a+e的总数等于6,b+c+d的总数等于3且b和c不同时为0,其条件是配位体(CHbFc(CF3)d)可以不同。
8.权利要求6和7的氟磷酸锂的用途,用作锂电池中的导电盐。
9.用于锂电池的电解质,包括权利要求6和7中的通式(I)的氟磷酸锂。
10.锂蓄电池,包括权利要求9的电解质。
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US7833660B1 (en) | 2006-09-07 | 2010-11-16 | The United States Of America As Represented By The Secretary Of The Army | Fluorohaloborate salts, synthesis and use thereof |
US7820323B1 (en) | 2006-09-07 | 2010-10-26 | The United States Of America As Represented By The Secretary Of The Army | Metal borate synthesis process |
DE102007004698A1 (de) | 2007-01-31 | 2008-08-07 | Merck Patent Gmbh | Verbindungen enthaltend Organofluorochlorophosphatanionen |
CA2680116A1 (en) * | 2007-03-08 | 2008-09-12 | Board Of Governors For Higher Education, State Of Rhode Island And The P Rovidence Plantations | Novel electrolyte for lithium ion batteries |
EP2297802A1 (en) * | 2008-07-03 | 2011-03-23 | The Board of Governors for Higher Education State of Rhode Island and Providence Plantations | Inhibition of electrolyte oxidation in lithium ion batteries with electrolyte additives |
DE102008035174A1 (de) | 2008-07-28 | 2010-02-11 | Merck Patent Gmbh | Verfahren zur Herstellung von Bis(fluoralkyl)-phosphinsäure oder Fluoralkylphosphonsäure |
DE102009058969A1 (de) * | 2009-12-18 | 2011-06-22 | Merck Patent GmbH, 64293 | Verbindung mit (Perfluoralkyl)fluorohydrogenphosphat - Anionen |
KR101621383B1 (ko) | 2009-12-22 | 2016-05-16 | 삼성에스디아이 주식회사 | 리튬 전지 |
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FR2606217B1 (fr) * | 1986-10-30 | 1990-12-14 | Elf Aquitaine | Nouveau materiau a conduction ionique constitue par un sel en solution dans un electrolyte liquide |
US4900854A (en) * | 1987-03-23 | 1990-02-13 | The Dow Chemical Company | Process for the preparation of asymmetrical alkaline earth metal organoborates, organoaluminates, organoarsenates, and organophosphates |
DE4316104A1 (de) * | 1993-05-13 | 1994-11-17 | Manfred Wuehr | Elektrolyt zur Anwendung in einer galvanischen Zelle |
WO1995026056A1 (fr) * | 1994-03-21 | 1995-09-28 | Centre National De La Recherche Scientifique | Materiau a conduction ionique presentant de bonnes proprietes anti-corrosion |
-
1996
- 1996-10-05 DE DE19641138A patent/DE19641138A1/de not_active Withdrawn
-
1997
- 1997-09-24 JP JP51712698A patent/JP3188478B2/ja not_active Expired - Fee Related
- 1997-09-24 AU AU47776/97A patent/AU4777697A/en not_active Abandoned
- 1997-09-24 AT AT97910341T patent/ATE198595T1/de not_active IP Right Cessation
- 1997-09-24 RU RU99108793/04A patent/RU2184738C2/ru not_active IP Right Cessation
- 1997-09-24 CN CN97198513A patent/CN1098270C/zh not_active Expired - Fee Related
- 1997-09-24 EP EP97910341A patent/EP0929558B1/de not_active Expired - Lifetime
- 1997-09-24 WO PCT/EP1997/005230 patent/WO1998015562A1/de active IP Right Grant
- 1997-09-24 KR KR19997002887A patent/KR100346821B1/ko not_active IP Right Cessation
- 1997-09-24 DE DE59702905T patent/DE59702905D1/de not_active Expired - Lifetime
- 1997-09-24 US US09/284,010 patent/US6210830B1/en not_active Expired - Lifetime
- 1997-09-24 CA CA002280938A patent/CA2280938C/en not_active Expired - Fee Related
- 1997-10-02 ZA ZA9708840A patent/ZA978840B/xx unknown
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2000
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Also Published As
Publication number | Publication date |
---|---|
ZA978840B (en) | 1998-04-24 |
WO1998015562A1 (de) | 1998-04-16 |
JP2001081096A (ja) | 2001-03-27 |
JP2000508340A (ja) | 2000-07-04 |
AU4777697A (en) | 1998-05-05 |
CA2280938C (en) | 2006-02-21 |
JP3625751B2 (ja) | 2005-03-02 |
CN1232465A (zh) | 1999-10-20 |
CA2280938A1 (en) | 1998-04-16 |
DE19641138A1 (de) | 1998-04-09 |
JP3450283B2 (ja) | 2003-09-22 |
KR100346821B1 (ko) | 2002-08-14 |
US6210830B1 (en) | 2001-04-03 |
EP0929558A1 (de) | 1999-07-21 |
JP3188478B2 (ja) | 2001-07-16 |
DE59702905D1 (de) | 2001-02-15 |
KR20010032713A (ko) | 2001-04-25 |
EP0929558B1 (de) | 2001-01-10 |
JP2001076757A (ja) | 2001-03-23 |
ATE198595T1 (de) | 2001-01-15 |
RU2184738C2 (ru) | 2002-07-10 |
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