CN1107354C - 用于电化学锂插入型的电极材料 - Google Patents
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- 239000007772 electrode material Substances 0.000 title claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 11
- 230000002687 intercalation Effects 0.000 title abstract 2
- 238000009830 intercalation Methods 0.000 title abstract 2
- 229910008722 Li2NiO2 Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910003005 LiNiO2 Inorganic materials 0.000 claims description 6
- 229910021543 Nickel dioxide Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 230000002427 irreversible effect Effects 0.000 abstract description 10
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 10
- 229910032387 LiCoO2 Inorganic materials 0.000 description 9
- 239000010406 cathode material Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 5
- 239000010405 anode material Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- -1 V2O5 Chemical class 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910008695 Li2Ni8O10 Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- MYWGVEGHKGKUMM-UHFFFAOYSA-N carbonic acid;ethene Chemical compound C=C.C=C.OC(O)=O MYWGVEGHKGKUMM-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
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- H—ELECTRICITY
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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
一种用于锂插入型电化学电池的电极材料。该电极材料为Li2NiO2材料，它可单独使用，也可与传统的锂化的过渡金属氧化物材料组合使用。该电极材料提供了锂离子的蓄积能力或过量的锂离子，以克服在现在的锂离子电池中通常产生的不可逆电容量损失。
Description
技术领域
本发明一般来说涉及用于电化学电池的电极和电极材料，特别是涉及适合作为锂插入型电化学电池的阴极的电极材料。
背景技术
为了在可充电的锂离子电池和锂聚合物电池中用作正电极或阴极，过去十年已广泛研究了许多种过渡金属氧化物材料。由于其重量能量密度，这些材料已被研究。其例证性过渡金属氧化物包括这样一些化合物，如V2O5、V6O13、TiO2、MnO2、LiCoO2、LiMn2O4和LiNiO2，这只是列举的少数几个例子。这样的材料可与负电极或阳极材料相组合，制成电化学电池。优选的阳极材料与所选的阴极材料有关，例如包括金属锂、锂合金以及锂插入型材料，如石墨。另一方面，基于无定形碳的材料，如在1995年9月27日提交的共同未决的美国专利申请书No.08/534427中公开的那些材料是可在电池中用作阳极的新型材料。
遗憾的是，碳材料用作负电极材料或阳极对电化学电池的设计提出了挑战。碳材料的初期充电牵涉到在碳颗粒上形成电化学界面膜。这一过程使电池的电容量有重大的不可逆损失。因为这一不可逆电容量的充电必需来自正电极，所以在第一次充电和放电循环过程中所产生的不可逆电容量损失使电池的总电容量显著下降。作为一个例子，如果材料的可逆电容量大约为300mAh/g，而它的不可逆电容量损失为120mAh/g，那么对于300mAh可利用的电容量来说，为了使1g阳极材料充电需要420mAh/g电容量。为了与负极电容量匹配，所以如果阴极材料的电容量约为120mAh/g，对于1g阳极材料来说需要大约3.5g阴极材料。
需要阴极有过量的电容量，以便克服阳极的不可逆电容量损失，这就使锂电池的尺寸、重量和价格都大大增加。因此，希望可将另外的锂离子源加到正极材料中并转移到阳极，以便补偿最初的不可逆电容量损失。用这种方法，可在对电池的尺寸、重量和价格没有不良影响的条件下显著地提高总的电容量。
发明内容
因此，需要一种可提供过量锂离子或蓄积锂离子的电极材料，以克服在锂插入型电池中阳极材料产生的显著不可逆电容量损失。在第一次循环后，电极材料在电化学上必需是活性的，以致不使加有这种材料的整个电池的性能变坏。而且，电极材料必需由在电池的其他组分存在下在电化学上是稳定的材料组成。
本发明涉及以下内容：
1.一种用于可充电电化学电池的电极，所述的电极含有式Li2NiO2的第一种电极材料和式LiNiO2的第二种电极材料，其中Li2NiO2和LiNiO2已在单独的反应中合成，然后物理混合制成电极活性材料，
其中所述的第一种电极材料占电极的15-35重量％。
附图说明
图1为包括本专利申请书公开的材料制成的电极的电化学电池的示图；
图2为本发明电极材料的X射线衍射图；
图3为使用本发明电极材料的电化学电池头10次循环电池电压的充电和放电曲线；
图4为使用本发明电极材料的电化学电池头20次循环电池电压的充电和放电曲线；
图5为使用加有本发明电极材料的电极头10次循环电化学电池的充电和放电曲线；
实施方式
虽然从说明书可推断出权利要求书所规定的本发明的特点是新颖的，但从以下说明并结合附图可进一步很好地理解本发明，其中使用相同的编号。
现参考图1，图中示意说明了电化学电池10，例如包括本发明电极材料的电极的电池或电化学电容器。电化学电池10包括正电极或阴极20、负电极或阳极30，以及其间设置的电解质40。电池的负电极或阳极30由碳或石墨型材料，如上述的材料制成。电池的阴极或正电极20至少含有本发明的材料，还可含有锂化的过渡金属氧化物。在电极之间的电解质40可为本专业已知的任何一种电解质，例如，非水液体电解质如LiPF6、LiClO4、LiBF4及其组合物。另一方面，电解质可以是由电解质活性物种分散在其中的聚合物载体结构物组成的固体电解质。在这一方面，电解质40例如可由聚环氧乙烷(PEO)作为聚合物载体结构物以及分散在其中的锂盐如LiClO4作为电解质活性物种组成。在这一实施方案中，电解质也可作为正电极和负电极之间的隔板。另外，电解质也可是含水的、非水的、固态的、凝胶的或其组合。然后将电极和电解质封装在包装物中，如电池壳或聚合物外壳中。
为了制作这样一种其中阴极有过量的锂离子或蓄积锂离子以便克服在第1次循环时阳极产生的不可逆电容量损失的电化学电池，必需提供有过量锂离子或蓄积锂离子的阴极材料。常规的阴极材料如LiMnO2、LiCoO2和LiNiO2没有这种过量的蓄积能力。因此，电极必需含有这样一种能有过量的蓄积能力材料。所以，阴极20应有“蓄积”材料，如Li2NiO2或Li4Co4O6，其中每一种都有大的初始充电电容量，可逆电容量与现有材料如LiCoO2和/或LiMn2O4相差不多。因此，该阴极材料含有传统的电极材料如LiCoO2或LiMn2O4与Li2NiO2和/或Li4Co4O2的混合物。在本发明一优选的实施方案中，Li4Co4O6和/或Li2NiO2占阴极的10-100％(重量)，更优选15-35％(重量)。
Li2NiO2可在惰性气氛中通过高温反应来合成。正如这里使用的，惰性气氛指氦气、氮气和/或氩气气氛。可用于制造过程的前体材料例如包括Ni(OH)2、Ni粉或NiO和LiOH。当使用Ni(OH)2和LiOH时，在升温下，即在约450℃以上的温度下，可能出现以下总的反应：
同样，如果使用NiO和LiOH作为原料，如下的反应可能出现：
显然其他的镍和锂盐也可用作原料，但上述材料是优选的，因为产物为所需的最终材料。也可使用其他盐如碳酸盐或硝酸盐，但此时可能生成Li2CO3。该物质在低于约700℃的温度下不分解，或者Ni2+离子也可氧化成高价，形成稳定的相如Li2Ni8O10。
上述反应在约500℃以上可以合理的速率出现。所以高于500℃的反应温度是优选的，但应控制到约850℃以下，因为在更高的温度下产物可能分解成Li2O和NiO。本发明可从以下实施例更好地理解。
实施例
将LiOH与Ni(OH)2按摩尔比2.15∶1通过传统的混合方法进行混合。将混合物在氮气气氛中在450℃下加热12小时。此后，将材料研磨和在氮气气氛中650℃下加热约50小时，其中进行两次间歇研磨过程。最终的产物为深绿色的，用图2所示的X射线衍射图(XRD)说明。CuαK1用作X射线源。XRD分析以横座标为2θ角和纵座标为强度作图。显然按上述制备的材料中有一些未反应的NiO和LiOH，但用图2所示的角度下的XRD特征峰可确定主要材料是Li2NiO2。具体地说，XRD图用在2θ角在26度处有很强的峰，在2θ角约20度处有次强峰来表征。
试验1
制作的Li2NiO2在电化学电池中作为正电极或阴极材料被测试，其中在阴极中Li2NiO2材料基本上构成100％活性材料。所用的负电极材料为锂箔，而电解质为1M LiPF6，50％碳酸亚乙酯(EC)和50％碳酸二亚乙酯(DEC)，以及玻璃织物隔板。
现参考图3，在这里说明用Li2NiO2作为阴极材料的电化学电池的充电和放电曲线。图3的研究表明，Li2NiO2材料的初始充电电容量为376mAh/g(线52)，而放电电容量为123mAh/g(线54)。初始充电电容量比传统的阴极材料如LiCoO2和LiMn2O4高得多。因此该材料具有为克服明显的不可逆电容量损失所需的内在Li离子蓄积能力。放电电容量也与传统的LiCoO2和LiMn2O4材料相差不多。第1次循环后，充电和放电曲线几乎变成对称的，从一个循环到另一循环基本上保持相同。因此，可以得出，该材料的电容量是十分稳定的。
试验2
如上述制作的Li2NiO2与传统的LiCoO2材料混合，制成电化学电池的正电极。该复合电极含有20％(重量)Li2NiO2和80％(重量)LiCoO2。锂箔在电池中用作负电极。电解质为试验1中使用的。
现参考图4，这里说明在试验2中描述的电化学电池的充电和放电曲线。该电池的初始充电电容量约为190mAh/g(线56)，按全部正电极材料计，而传统的LiCoO2为约130mAh/g。因此，在充电时复合材料提供了新增60mAh/g电容量。放电电容量约为120mAh/g(线58)，它与传统的材料相差不多。图4的研究表明，第1次循环后，电池的电容量是十分稳定的。
试验3
如上面试验2所述的复合正电极与石墨作为负电极以及试验1的电解质配合使用。
现参考图5，这里说明试验3的电化学电池的充电和放电曲线。图5说明，对于该试验电池来说，基于全部复合正电极材料，如线60和62所示，得到的电容量为120mAh/g。正如可从图5中得出的，电池的电容量是十分稳定的。
虽然已说明了本发明的优选实施方案，但应当清楚，这不是对本发明的限制。对于熟悉本专业的技术人员来说，在不违背附后的权利要求书规定的本发明的精神实质和范围的条件下，可有许多改进、改变、变通方案、替代方案和等效方案。
Claims (1)
1.一种用于可充电电化学电池的电极，所述的电极含有式Li2NiO2的第一种电极材料和式LiNiO2的第二种电极材料，其中Li2NiO2和LiNiO2已在单独的反应中合成，然后物理混合制成电极活性材料，
其中所述的第一种电极材料占电极的15-35重量％。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US57917995A | 1995-12-27 | 1995-12-27 | |
| US08/579,179 | 1995-12-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1206501A CN1206501A (zh) | 1999-01-27 |
| CN1107354C true CN1107354C (zh) | 2003-04-30 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96199387A Expired - Lifetime CN1107354C (zh) | 1995-12-27 | 1996-12-16 | 用于电化学锂插入型的电极材料 |
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| Country | Link |
|---|---|
| US (1) | US5759719A (zh) |
| EP (1) | EP0870339B1 (zh) |
| JP (1) | JP2000502831A (zh) |
| KR (1) | KR19990076829A (zh) |
| CN (1) | CN1107354C (zh) |
| CA (1) | CA2240844A1 (zh) |
| DE (1) | DE69631900T2 (zh) |
| WO (1) | WO1997024773A1 (zh) |
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| KR102268176B1 (ko) * | 2017-08-28 | 2021-06-22 | 주식회사 엘지에너지솔루션 | 리튬 이차전지 |
| PL3604229T3 (pl) | 2017-11-17 | 2023-07-17 | Lg Energy Solution, Ltd. | Sposób wytwarzania nieodwracalnego dodatku zawartego w materiale katody dla akumulatora litowego, materiał katody zawierający tak wytworzony nieodwracalny dodatek oraz akumulator zawierający materiał katody |
| KR102658855B1 (ko) * | 2018-10-18 | 2024-04-17 | 주식회사 엘지에너지솔루션 | 리튬 이차전지용 양극 첨가제의 제조방법 및 이로부터 제조된 리튬 이차전지용 양극 첨가제 |
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- 1996-12-16 KR KR1019980704955A patent/KR19990076829A/ko active IP Right Grant
- 1996-12-16 EP EP96945094A patent/EP0870339B1/en not_active Expired - Lifetime
- 1996-12-16 CN CN96199387A patent/CN1107354C/zh not_active Expired - Lifetime
- 1996-12-16 WO PCT/US1996/020765 patent/WO1997024773A1/en active IP Right Grant
- 1996-12-16 DE DE69631900T patent/DE69631900T2/de not_active Expired - Lifetime
- 1996-12-16 JP JP9524558A patent/JP2000502831A/ja active Pending
- 1996-12-16 CA CA002240844A patent/CA2240844A1/en not_active Abandoned
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| US4340652A (en) * | 1980-07-30 | 1982-07-20 | The United States Of America As Represented By The United States Department Of Energy | Ternary compound electrode for lithium cells |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO1997024773A1 (en) | 1997-07-10 |
| JP2000502831A (ja) | 2000-03-07 |
| US5759719A (en) | 1998-06-02 |
| EP0870339B1 (en) | 2004-03-17 |
| CA2240844A1 (en) | 1997-07-10 |
| EP0870339A1 (en) | 1998-10-14 |
| DE69631900D1 (de) | 2004-04-22 |
| CN1206501A (zh) | 1999-01-27 |
| DE69631900T2 (de) | 2004-08-05 |
| KR19990076829A (ko) | 1999-10-25 |
| EP0870339A4 (en) | 1999-12-15 |
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