CN1612380A - 一种可再充电的电化学元件的制备方法以及这种元件 - Google Patents

一种可再充电的电化学元件的制备方法以及这种元件 Download PDF

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CN1612380A
CN1612380A CNA2004100880864A CN200410088086A CN1612380A CN 1612380 A CN1612380 A CN 1612380A CN A2004100880864 A CNA2004100880864 A CN A2004100880864A CN 200410088086 A CN200410088086 A CN 200410088086A CN 1612380 A CN1612380 A CN 1612380A
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lithium
indium
negative electrode
positive electrode
electrode
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K·霍尔
A·佩尔纳
H·瓦纳
K·阿卡
R·亨里希
A·约尔斯
D·伊利克
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VARTA Microbattery GmbH
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
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    • H01M4/366—Composites as layered products
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
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    • H01M2300/0025—Organic electrolyte
    • 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
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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

在外壳(1)内具有由锂/铟合金组成的负电极(3)并具有锂－嵌入正电极(5)的可再充电电化学元件的制备方法中，主要由铟组成的负电极，带有含锂活性化合物的不带电的正电极以及电解质被引入到外壳内。通过元件的后续形成，形成了锂/铟负电极。例如，负电极的至少90％由铟组成。其中M为Ni、Co、Mn的LiMOx化合物用作正电极材料，并可能掺杂金属Al、Ti、Mg、Zn、Cr中的一种或多种。

Description

一种可再充电的电化学 元件的制备方法以及这种元件
技术领域和现有技术
本发明的主题是一种在外壳内具有由锂/铟合金组成的负电极并具有锂-嵌入正电极的可再充电的电化学元件的制备方法，以及这样的电化学元件。
以锂作为负电极材料的可再充电电化学元件，在各种实施方式中是广为人知的。这些元件的负电极通常由锂/铝合金或锂/铟合金构成。
例如，DE3816199A1描述了这种情况下负电极是怎样以两层电极的形式并由锂/铝合金层和铝合金层组成的。所谓的LiMOx材料通常以氧化物的形式用作正电极。这种情况下，M一般可以是Co、Ni、Mn，其可能掺杂有例如Al、Ti、Mg、Zn、Cr等。用作负活性材料的锂合金必须通过复杂的制造过程生产，例如通过在惰性气体气氛和压力下的高温合成。这种合成要大量消耗时间并是昂贵的。
目的和解决途径
本发明基于的目的是提供一种具有由锂/铟合金组成的负电极并具有锂-嵌入正电极的电化学元件的制备方法，并意图使这种制备方法简单化。
通过具有权利要求1的技术特征的方法和具有权利要求6的技术特征的电化学元件达到这一目的。本发明的有利的或优选的改进在进一步的权利要求中得以说明，并在下文中得到更详细的描述。权利要求的用词以明确引用的方式包括在说明书的内容中。
由于正电极中所用的材料也就是LiMOx，其中M是Co、Ni、Mn，其可能掺杂有例如Al、Ti、Mg、Zn、Cr等，是不带电的，因此，在形成过程中或在第一充电阶段锂离子从正电极迁移到负铟电极处。锂在那里沉积并形成锂/铟合金。尤其是，其可能是锂/铟涂层。例如，该过程可描述如下：
该过程是高度可逆的并具有高能量密度。
这里描述的系统可用于带有有机液体电解质的电池中，例如锂钮扣电池，锂柱形电池和锂绕制电池。它也可用于带有固体或聚合物电解质的电池，例如锂聚合物电池中。
这些特征和进一步的特征在权利要求中以及说明书和附图中，都是明显的，其中独立的特征每个都可以独立地实施，也可以彼此结合以本发明的一个实施方式的再组合的形式实施，并且在其它领域，可代表有利的实施方式以及本身可取得专利的并在这里要求保护的实施方式。本申请细分成的单独部分以及中间的标题不会限制这里所作的陈述的一般适用性。
附图简述
附图1是本发明钮扣电池形状的简单说明。其中标记1为电池外壳，2、6分别为导体网，3、5分别为负电极和正电极，4为电池隔板。
下文将对本发明作更详细的解释，尤其通过图1中简略说明的钮扣电池形式的可再充电元件的制备实施例来作说明。
具体实施方式详述
根据本发明，将带有由不锈钢或铝组成的输出导体网2的不带电正电极5引入到电池外壳1内，该正电极包含以锂相作为活性材料的材料，或者包含其中掺入锂的材料。该材料例如是LiMOx，其中M是Co、Ni或Mn，其可能带有金属掺杂例如Al、Ti、Mg、Zn、Cr等。
而且，电池外壳1中包含带有含锂导电盐(LiPF6，LiCIO4，LiBF4等)的有机液体电解质，固体电解质(例如沸石)或聚合物电解质(例如PEO、PVDF、PAN)。它可能也包含隔板4(例如由PP、PE、PTFE、PVDF组成)和负铟电极3，该负极以薄片或者如图1所示以粉末嵌入。该粉末可与普通粘结剂(PVDF、PTFE等)以及与导电碳黑混合。该负铟电极也可位于输出导体网6之上。引入电池外壳内的负电极包含高百分比的铟，例如超过70％，优选至少90％，尤其优选至少99％的铟。
通过这种方式制备的锂可再充电电池具有不带电的正电极5和负铟电极3。同传统的石墨负电极相比较，这种铟电极具有较高的比容量(石墨：372mAh/g)，其大概是高出其3倍的比容量。在这种锂离子可再充电电池中相当高的能量密度因此是可能的。
另外带有具有高铟成分负电极的锂可再充电电池可以更容易地制备。铟电极3可以薄片或者粉末，可能连同普通粘结剂例如PTFE或PVDF一起引入到电池外壳内。当在合金电极的情况下，无需复杂的阳极制法或合成。
为了制备本发明的钮扣电池(尺寸：直径：20mm；高度：2.5mm)，将直径16mm的100μm厚的铟薄片作为负电极在常压下压入到钮扣电池外壳内的由不锈钢网组成的输出导体网内。这种情况下，铟也可以是与导电物质例如MCMB(中碳微珠(Mesocarbon Microbeads))混合的粉末形式，也可以是片剂形式，或者可以在适当的输出导体网上被涂覆并作为涂覆薄片引入到电池中。根据尺寸计算出的该负电极的容量是500mAh/g。
然后将PP隔板放置在铟，例如Celgard2500，和无纺物，例如KodoshiP334上。
取决于其应用，由环状碳酸酯(例如碳酸亚乙酯)和开链碳酸盐(例如碳酸二乙酯)以1∶1到2∶8的混合物比例组成的溶剂混合物可用作电解质。将六氟合磷酸锂溶解到电解质中作为导电盐。
带有普通粘结剂(PVDF，PTFE)和与其混合并涂覆到铝输出导体网上的导电碳黑的LiCoO2(90％LiCoO2，4％碳黑，6％粘结剂)用于正电极。正电极被压印成片剂形式(400-600mg)并用电解质将其浸透，插入到电池外壳的电池容器内。该外壳和该容器连接在一起，并封闭电池。然后完成的电池在最高4.2V下用1C充电。这种情况下，用一个例子来解释，1C意味着如果电池容量是0.5Ah，则1C相应于0.5A。该值是所谓的经验值，并未被科学地定义，但在实践中经常使用。
用这种形式或充电步骤形成了锂/铟合金。该正电极中的锂在过程中迁移到负电极，并在铟上形成涂层或合金。
在形成过程中锂/铟合金的形成如下：
该制法允许制备的电池达到100％放电深度(DOD)150个循环，20％放电深度850个循环，并具有远高于石墨电极的能量密度。

Claims (6)

1、在外壳(1)内具有由锂/铟合金组成的负电极(3)并具有锂-嵌入正电极(5)的可再充电电化学元件的制备方法，其特征在于将主要由铟组成的负电极(3)，带有含锂活性化合物的不带电的正电极以及电解质引入到外壳(1)内，并通过元件的后续形成，形成了锂/铟负电极。
2、如权利要求1所述的方法，其特征在于负电极(3)的至少70％，优选至少90％是铟。
3、如权利要求1或2所述的方法，其特征在于负电极(3)的至少95％是铟。
4、如前述任一权利要求所述的方法，其特征在于带有含锂活性化合物的正电极(5)具有来自Ni、Co、Mn的元素M，其中尤其是，使用LiMOx的形式的带有元素M的化合物。
5、如权利要求4所述的方法，其特征在于LiMOx化合物掺杂了至少一种来自Al、Ti、Mg、Zn、Cr的金属。
6、在外壳(1)内具有由锂/铟合金组成的负电极并具有锂-嵌入正电极(5)的可再充电电化学元件，其特征在于该元件使用权利要求1-5中任一个方法制备。
CNA2004100880864A 2003-09-19 2004-09-17 一种可再充电的电化学元件的制备方法以及这种元件 Pending CN1612380A (zh)

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DE10219425A1 (de) * 2002-05-02 2003-11-20 Varta Microbattery Gmbh Verfahren zur Herstellung eines wiederaufladbaren galvanischen Elements
US8673493B2 (en) 2012-05-29 2014-03-18 Toyota Motor Engineering & Manufacturing North America, Inc. Indium-tin binary anodes for rechargeable magnesium-ion batteries
US8647770B2 (en) 2012-05-30 2014-02-11 Toyota Motor Engineering & Manufacturing North America, Inc. Bismuth-tin binary anodes for rechargeable magnesium-ion batteries
US9012086B2 (en) 2013-03-05 2015-04-21 Toyota Motor Engineering & Manufacturing North America, Inc. Active material for rechargeable magnesium ion battery

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JPS54141949A (en) * 1978-04-24 1979-11-05 Toyota Motor Corp Driver for automobile
EP0166260B1 (en) * 1984-05-31 1987-11-04 Hitachi Maxell Ltd. Lithium secondary battery
FR2615328A1 (fr) * 1987-05-12 1988-11-18 Bridgestone Corp Pile electrique et procede de fabrication
US6022640A (en) * 1996-09-13 2000-02-08 Matsushita Electric Industrial Co., Ltd. Solid state rechargeable lithium battery, stacking battery, and charging method of the same
JPH11219722A (ja) * 1998-02-03 1999-08-10 Matsushita Electric Ind Co Ltd リチウム二次電池
JP4578684B2 (ja) * 1998-11-10 2010-11-10 パナソニック株式会社 リチウム二次電池
US6998069B1 (en) * 1999-12-03 2006-02-14 Ferro Gmbh Electrode material for positive electrodes of rechargeable lithium batteries
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