CN103887561A - 锂离子二次电池用的电解液添加剂以及锂离子二次电池 - Google Patents
锂离子二次电池用的电解液添加剂以及锂离子二次电池 Download PDFInfo
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- CN103887561A CN103887561A CN201210581404.5A CN201210581404A CN103887561A CN 103887561 A CN103887561 A CN 103887561A CN 201210581404 A CN201210581404 A CN 201210581404A CN 103887561 A CN103887561 A CN 103887561A
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- lithium rechargeable
- rechargeable battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 8
- 239000002000 Electrolyte additive Substances 0.000 title abstract 3
- 239000003792 electrolyte Substances 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 49
- 229910052744 lithium Inorganic materials 0.000 claims description 73
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 68
- 239000000654 additive Substances 0.000 claims description 46
- 230000000996 additive effect Effects 0.000 claims description 46
- 238000005868 electrolysis reaction Methods 0.000 claims description 35
- -1 Nitrogenous organo-lithium compound Chemical class 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000000853 adhesive Substances 0.000 claims description 12
- 230000001070 adhesive effect Effects 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 11
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
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- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
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- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
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- PBGGNZZGJIKBMJ-UHFFFAOYSA-N di(propan-2-yl)azanide Chemical compound CC(C)[N-]C(C)C PBGGNZZGJIKBMJ-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010936 titanium Substances 0.000 claims description 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
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- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
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- 239000010949 copper Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
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- 150000004772 tellurides Chemical class 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims 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 claims 1
- 150000004771 selenides Chemical class 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 9
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- 238000005227 gel permeation chromatography Methods 0.000 description 12
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- 239000007785 strong electrolyte Substances 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
本发明提供一种锂离子二次电池用的电解液添加剂,其包括有机锂化合物和超分歧结构材料。所述电解液添加剂使得电解液的分解电压高达5.5V,且可提升电解液热耐受温度达至少10℃,能大幅增进电池的安全性。本发明亦提供一种锂离子二次电池。
Description
技术领域
本发明是有关于锂离子二次电池用的电解液添加剂以及锂离子二次电池。
背景技术
现代可携式电子装置几乎完全依赖可充电的锂离子二次电池当成其电源。这种需求驱策增加其电容量能力、电源能力、使用寿命、安全特性及降低成本的各种不断的研发努力。
锂离子二次电池的安全问题主要来自电池内部温度升高,包括电池不当加热、过度充电、正负极材料接触造成短路等。当电池内部温度持续升高且无法抑制时,分开正负极材料用的隔离膜就会开始熔化、穿破,而导致大量电流短路,然后电池就会加速变热。当电池温度上升至180℃以后会引发电解液与正极材料的分解反应,产生剧热及喷出大量气体,引发起火燃烧及爆炸等危险。
由此可知,锂离子二次电池的安全性与电解液受到热扰动而破坏动态缓冲效能体系的温度、以及电解液的分解电压相关。当电解液受到热扰动而破坏动态缓冲效能体系的温度越高(表示耐高温能力越好),电解液的分解电压越大(表示耐过度充电的能力越好),锂离子二次电池的安全性越佳。因此,需要一种可以增进锂离子二次电池的安全性的电解液添加剂,以确保消费者的使用安全。
发明内容
本发明的目的在于提供一种可以增进锂离子二次电池的安全性的电解液添加剂。
本发明提供一种锂离子二次电池用的电解液添加剂,其包括含氮的有机锂化合物和超分歧结构材料。
本发明亦提供一种锂离子二次电池,其包括:正极、负极、隔离膜、电解液;以及电解液添加剂,所述的电解液添加剂包括含氮的有机锂化合物以及超分歧结构材料。
本发明的优点在于:本发明的锂离子二次电池用的电解液添加剂使得电解液的分解电压高达5.5V,且可提升电解液热耐受温度达至少10℃,能大幅增进电池的安全性。
为让本发明的上述特征和优点能更明显易懂,下文特举实施例,并配合所附附图作详细说明如下。
附图说明
图1为依据本发明一实施例所绘示的锂离子二次电池用的电解液添加剂的示意图;
图2为实施例1的含有机锂的超分歧结构材料的GPC图;
图3为实施例2的含有机锂的超分歧结构材料的GPC图;
图4为实施例3、实施例4及比较例1的碳酸丙烯酯的自扩散系数的同位1H-NMR的变温检测;
其中,主要元件符号说明:
10:电解液添加剂 12:有机锂化合物
14:超分歧结构材料 16:孔洞。
具体实施方式
图1为依据本发明一实施例所绘示的锂离子二次电池用的电解液添加剂的示意图。请参照图1,本发明的锂离子二次电池用的电解液添加剂10包括有机锂化合物12以及超分歧结构材料14。本文中,有机锂化合物与超分歧结构材料结合构成的材料称为“含有机锂的超分歧结构材料”。
如图1所示,有机锂化合物12例如物理吸附于超分歧结构材料14的孔洞(pore)16内或超分歧结构材料14的表面上。有机锂化合物12与超分歧结构材料14之间并无化学键结,但由于两者之间的氢键或范德华力作用,超分歧结构材料14可捕获(trap)有机锂化合物12于其内。其中,超分歧结构材料的粒径(particle size diameter)约为50nm,有机锂化合物的粒径约为0.3~3nm,孔洞尺寸(pore size)约为1~10nm。
术语“有机锂化合物”为非锂盐型的含锂有机化合物。具体言之,本发明的有机锂化合物不会被电解液解离。在一实施例中,有机锂化合物为含氮的有机锂化合物,其中锂元素接在氮元素上。此外,所述含氮的有机锂化合物还包括硅、硫、氧中的至少的一个元素。换言之,本发明的有机锂化合物可为含氮的有机锂化合物、含氮/硅的有机锂化合物、含氮/硫的有机锂化合物或含氮/氧的有机锂化合物。
有机锂化合物中锂元素的数量n可为一个或多个,本发明并不对锂元素的数量n做限制。在一实施例中,有机锂化合物由式(1)至式(6)其中之一表示:
Li—N——R1 n=1 式(1)
其中R1包括甲基(methyl)、乙基(ethyl)、丙基(propyl)、异丙基(isopropyl)、丁基(butyl)或苯基(phenyl);以及R2~R16各自独立地包括甲基、乙基、丙基、异丙基、丁基、苯基、二异丙基酰胺基(diisopropy lamide)、-p-(三级丁基)3(-p-(t-Butyl)3)或-p-(苯基)3(-p-(phenyl)3)。-p-(三级丁基)3或-p-(苯基)3的具体结构式如下所示:
举例来说,当锂元素的数量n为1时,有机锂化合物的具体化合物可呈现如式(7)至式(8)。当锂元素的数量n为2时,有机锂化合物的具体化合物可呈现如式(9)。
式(7)
双(三氟甲烷磺酰)亚胺锂
(lithium bis(trifluoromethanesulfonyl)amide;LiTFSA)
[Tokyo Chemical Industry Co.](CAS NO:90076-65-6)
四甲基哌啶锂
(lithium tetramethyl piperidide)
[FMC Lithium](CAS NO:38227-87-1)
式(9)
双(三甲硅基)酰胺化锂;六甲基二硅基酰胺化锂
(lithium bis(trimethylsilyl)amide;lithium hexamethyldisilazide)
[Sigma-Aldrich Co.LLC](CAS NO:4039-32-1)
在一实施例中,有机锂化合物可自行合成。
术语“超分歧结构材料”为含氮的超分歧高分子(hyper-branched polymer),其至少具有三个分歧点,且分歧度(degree ofbranching;DB)至少大于50%。
本发明的超分歧结构材料的单体选自由马来酰亚胺(maleimide)、双马来酰亚胺(bismaleimide)、多马来酰亚胺(multi-maleimide)、巴比土酸(barbituricacid)、咪唑(imidazole)、吡咯(pyrrole)、吡啶(pyridine)、哒嗪(pyridazine)、嘧啶(pyrimindine)、吡嗪(pyradine)、三嗪(triazine)及其衍生物所组成的群组中的至少一种。
举例来说,双马来酰亚胺可由式(10)表示,多马来酰亚胺可由式(11)表示,且巴比土酸可由式(12)表示。
式(10)
4,4'-二苯甲烷双马来酰亚胺(BMI-1000)
(4,4'-diphenylmethane bismaleimide)
[Hakuei&Co.,Ltd](CAS No:13676-54-5)
苯甲烷马来酰亚胺的寡聚合物(BMI-2300)
(oligomer of pheny lmethane maleimide)
[Daiwakasei Industry Co.,Ltd](CAS NO:67784-74-1)
巴比土酸(BTA)
(barbituric acid)
[Alfa Aesar](CAS NO:67-52-7)
此外,所述有机锂化合物与所述超分歧结构材料的重量比为约1:99~99:1,例如约1:4~4:1。
电解液及其制备方法
本发明的电解液包括锂盐、有机溶剂及如上所述的电解液添加剂,其中电解液添加剂占电解液总重的约0.1wt%至10wt%,例如约0.5wt%至5wt%。
锂盐包括LiPF6、LiClO4、LiBF4、LiSO3CF3、LiN(SO2CF3)2、LiN(SO2CF2CF3)2、LiTFSI、LiAsF6、LiSbF6、LiAlCl4、LiGaCl4、LiNO3、LiC(SO2CF3)3、LiSCN、LiO3SCF2CF3、LiC6F5SO3、LiO2CCF3、LiSO3F、LiB(C6H5)4、LiB(C2O4)2或其组合。锂盐的浓度为0.5至1.5摩尔/升(M)。
有机溶剂包括碳酸酯类(carbonate)、酯类(ester)、醚类(ether)、酮类(ketone)或其组合。所述酯类选自由乙酸甲酯(methyl acetate)、乙酸乙酯(ethyl acetate)、丁酸甲酯(methyl butyrate)、丁酸乙酯(ethyl butyrate)、丙酸甲酯(methyl proionate)、丙酸乙酯(ethyl proionate)及乙酸丙酯(propylacetate;PA)所组成的族群。所述碳酸酯类包括碳酸乙烯酯(ethylene carbonate;EC)、碳酸丙烯酯(propylene carbonate;PC)、碳酸二乙酯(diethyl carbonate;DEC)、碳酸甲基乙基酯(ethyl methyl carbonate;EMC)、碳酸二甲酯(dimethylcarbonate;DMC)、碳酸亚乙烯酯(vinylene carbonate)、碳酸丁烯酯(butylenecarbonate)、碳酸二丙酯(dipropyl carbonate)或其组合。
电解液溶剂配比可藉由进行电解液三种有机溶剂碳酸二乙酯(DEC)、碳酸乙烯酯(EC)、碳酸丙烯酯(PC)扩散系数的NMR-1H检析,取得较佳比例。将DEC、EC、PC三种有机溶剂以单成分、双成分、多成分表示并且设计十七个测试点进行NMR扩散值(diffusion)测量。根据实验数据趋势分析,有机溶剂间存有不同程度的交互作用(interaction),使得溶剂本体的自我扩散行为受到牵制而减降其速率,且三种溶剂系统的牵制作用又较两种溶剂系统为大,且具有一致性相对的减降效应;其中若以三种溶剂组合做选配考虑,则以DEC:EC:PC的组合比率(重量)为5:3:2时,具有较高的扩散系数,其值大约在12.5×10-10m2/sec附近。
在本发明的电解液中,藉由添加作为电解液添加剂的含有机锂的超分歧结构材料,可使得电解液的分解电压高达5.5V,且可提升电解液受到热扰动而破坏动态缓冲效能体系的温度达至少10℃,能大幅增进电池的安全性。
制备电解液的方法包括将多种有机溶剂,以特定的重量比率混合以形成混合溶液。然后,将特定浓度的锂盐加入此混合溶液中。接着,加入上述含有机锂的超分歧结构材料作为电解液添加剂,其中电解液添加剂占电解液总重的约0.1wt%至10wt%。
锂离子二次电池及其制备方法
锂离子二次电池包括正极、负极、隔离膜与电解液。电解液的制备如上所述,于此不再赘述。
正极浆料为80~94%的正极活性物、3~15%的导电性添加物与3~10%的正极粘合剂溶于N-甲基-2-咯烷酮(NMP)中,而后将其均匀涂布于长300米、宽35厘米、厚20μm的铝箔卷,干燥后的正极卷施予辗压及分条,最后将其以摄氏110度真空干燥4小时,得到一正极。正极活性物可为钒、钛、铬、铜、钼、铌、铁、镍、钴与锰等金属的锂化氧化物、锂化硫化物、锂化硒化物、锂化碲化物或其混合物。导电性添加物可为碳黑、石墨、乙炔黑、镍粉、铝粉、钛粉、不锈钢粉及其混合物。正极粘合剂可为氟树脂粘合剂,例如聚偏二氟乙烯(polyvinylidene fluoride,PVDF)、铁氟龙(Teflon)、苯乙烯丁二烯橡胶(styrene-butadiene rubber)、聚酰胺树脂(polyamide)、三聚氰胺树脂(melamineresin)、羧甲基纤维素(carboxymethylcellulose,CMC)粘合剂。
负极浆料则为直径1~30μm的90%~97%的负极活性物与3~10%的负极粘合剂溶于N-甲基-2-咯烷酮(NMP)中,搅拌均匀后涂布于长300米、宽35厘米、厚10μm的铜箔卷,所形成的负极卷经辗压分条后,同样以摄氏110度真空干燥4小时,得到一负极。负极活性物可以是介稳相球状碳(MCMB)、气相成长碳纤维(VGCF)、纳米碳管(CNT)、焦炭、碳黑、石墨、乙炔黑、碳纤维和玻璃质碳、锂合金或其混合物。负极活性物可进一步包括金属氧化物如SnO、SnO2、GeO、GeO2、In2O、In2O3、PbO、PbO2、Pb2O3、Pb3O4、AgO、Ag2O、Ag2O3、Sb2O3、Sb2O4、Sb2O5、SiO、ZnO、CoO、NiO、FeO、TiO2、Li3Ti5O12或上述的组合。负极粘合剂可为氟树脂粘合剂,例如聚偏二氟乙烯(PVDF)、铁氟龙(Teflon)、苯乙烯丁二烯橡胶、聚酰胺树脂、三聚氰胺树脂或羧甲基纤维素(CMC)粘合剂。
或者,当金属片直接作为负极時,负极材料可为Al、Zn、Bi、Cd、Sb、Si、Pb、Sn、Li3FeN2、Li2.6Co0.4N、Li2.6Cu0.4N或上述的组合。
隔离膜为厚度15~20μm的聚丙烯/聚乙烯/聚丙烯(PP/PE/PP)三层膜。
制备锂离子二次电池的方法包括将正极、负极与隔离膜一起卷绕、辗压后,放入具有尺寸为38mm x3.5mm x62mm的铝箔袋长方体外壳中。然后,注入如上所述的电解液。
以下,将列举多个实施例及比较例以验证本发明的功效。
制备电解液添加剂
实施例1
取200克的碳酸丙烯酯(PC;Propylene Carbonate―99%,购自Alfa Aesar)置入于500ml的四孔圆底烧瓶(一孔接冷凝管,一孔接温度探针)内并通入氮气及加温至130°C后,加入12.5078克的巴比土酸(BTA,Barbituricacid―99%,购自Alfa Aesar,CAS编号67-52-7),于130℃的碳酸丙烯酯中搅拌20分钟使之溶解。之后,再将34.9922克的双马来酰亚胺(BMI,BMI-1000;4,4’-diphenylmethane bismaleimide―>95%,购自Hakuei&Co.,Ltd,CAS编号13676-54-5)加入并持续搅拌使其溶解及进行反应,其中BMI-1000与BTA的摩尔比为1:1。待BMI-1000与BTA在130°C的PC内作用反应3小时后,再加入2.5克的双(三甲硅基)酰胺化锂(Lithium Bis(trimethylsilyl)amide,购自Sigma-Aldrich Co.LLC,CAS编号4039-32-1)并持续搅拌使其溶解及进行反应至15小时。至此,制得实施例1的含有机锂的超分歧结构材料,其中总固含量占所得溶液的20wt%,且有机锂占总固含量的5wt%。
实施例2
取200克的碳酸丙烯酯(PC;Propylene Carbonate―99%,购自Alfa Aesar)置入于500ml的四孔圆底烧瓶(一孔接冷凝管,一孔接温度探针)内并通入氮气及加温至130°C后,加入38.1770克的双马来酰亚胺(BMI;BMI-1000;4,4’-diphenylmethane bismaleimide―>95%,购自Hakuei&Co.,Ltd,CAS编号13676-54-5),于130°C的碳酸丙烯酯中搅拌15分钟使之溶解。之后,再将6.8230克的巴比土酸(BTA;Barbituric acid―99%,购自Alfa Aesar,CAS编号67-52-7)分四批次加入(每次间隔15分钟)并持续搅拌使其溶解及进行反应,其中BMI-1000与BTA的摩尔比为2:1。待四批次BTA添加完后,再使BMI-1000与BTA在130°C的碳酸丙烯酯内持续作用反应15分钟后,再加入5.0克的双(三氟甲烷磺酰)亚胺锂(Lithium bis(trifluoromethanesulfonyl)amide,购自Tokyo Chemical Industry Co.,CAS编号90076-65-6)并持续搅拌使其溶解及进行反应至4小时。至此,制得实施例2的含有机锂的超分歧结构材料,其中总固含量占所得溶液的20wt%,且有机锂占总固含量的10wt%。
将实施例1及实施例2的含有机锂的超分歧结构材料进行凝胶渗透层析法(Gel Permeation Chromatography;GPC)检析,其中选用DMF溶剂回流系统的凝胶液相层析仪系统。GPC测试检析条件为管柱系统(column system):KDG/KD-801/KD-802/KD-802/KD-802.5;管柱分析温度(column oventemperature):40℃;以及流量(flow rate):0.8ml/min。
图2为实施例1的含有机锂的超分歧结构材料的GPC图,其GPC尖峰时间为26.465分钟。图3为实施例2的含有机锂的超分歧结构材料的GPC图,其GPC尖峰时间为26.698分钟。
图2及图3的GPC检析结果对应本发明的图1的示意图。在本发明的含有机锂的超分歧结构材料中,有机锂化合物与超分歧结构材料之间并无化学键结,但由于两者之间的氢键或范德华力作用,超分歧结构材料可捕获有机锂化合物于其内,而呈现为一整体。因此,GPC检析结果仅显示一个尖峰时间(即含有机锂的超分歧结构材料),而非多个分开的尖峰时间。
制备电解液
实施例3
电解液组成是1.2M的LiPF6溶于碳酸丙烯酯(PC)、碳酸乙烯酯(EC)与碳酸二乙酯(DEC)混合溶剂(重量比EC/PC/DEC=3/2/5),电解液添加剂为0.5wt%的实施例1的含有机锂的超分歧结构材料。至此,制得实施例3的电解液。
实施例4
电解液组成是1.2M的LiPF6溶于碳酸丙烯酯(PC)、碳酸乙烯酯(EC)与碳酸二乙酯(DEC)混合溶剂(重量比EC/PC/DEC=3/2/5),电解液添加剂为2wt%的实施例2的含有机锂的超分歧结构材料。至此,制得实施例4的电解液。
比较例1
电解液组成是1.2M的LiPF6溶于碳酸丙烯酯(PC)、碳酸乙烯酯(EC)与碳酸二乙酯(DEC)混合溶剂(重量比EC/PC/DEC=3/2/5),但未使用任何电解液添加剂。至此,制得比较例1的电解液。
未加入LiPF6锂盐之前,EC/PC/DEC溶剂系统中各溶剂本身会受到其它溶剂成分的交互作用影响,并达到牵制的动态平衡。加入LiPF6锂盐之后,整个DEC/EC/PC溶剂系统的动态平衡即受到明显的牵动变化,导致形成另一个牵制的动态平衡,且各组份溶剂的扩散系数会有较明显的差异,亦即可观察到强电解质的锂盐与有机溶剂间会形成不同程度的溶剂配位(solvationcoordination)。
在有/无添加作为电解液添加剂的含有机锂的超分歧结构材料之后,将实施例3、实施例4、比较例1的电解液进行核磁共振光谱(Nuclear MagneticResonance Spectroscopy;NMR)检析,其中选用高解析的液态BrukerAvance-400及Varian INOVA-500NMR。进行PC-1H位置扩散(diffusion)系数的同位(in-situ)1H-NMR的变温检测(30℃~110℃),其检析结果如表1及图4所示。
表1
如表1及图4结果显示,比较例1的电解液在温度超过70℃时,PC-1H的扩散系数有明显的上升现象,显示电解液中的溶剂与锂盐相互牵制作用所形成的缓冲稳态平衡受热干扰而破坏,溶剂回归倾向个体运动,此将使整个电解液体系无法维系电化学的稳态作用机制,并在溶液中形成诸多电双层结构,造成内阻值大幅增加,会减降电池的总体性能。反观实施例3、实施例4的电解液的测试结果,在添加含有机锂的超分歧结构材料后,能使提升电解液受到热扰动而破坏动态缓冲效能体系的温度,添加0.5wt%(实施例3)可提升约10℃,而添加2wt%(实施例4)则可提升约30℃。
制备锂半电池
实施例5
组2颗钮扣型半电池(尺寸CR2032),其中电池正极采用氧化锂钴(LiCoO2)(其中LiCoO2:超级导电碳黑(super Pcarbon black):聚偏二氟乙烯粘着剂(PVDF binder)=94:3:3(重量比)),负极采用锂金属,隔离膜采用聚丙烯/聚乙烯/聚丙烯(PP/PE/PP)三层膜(商品名Celgard2325),且电解液组成采用实施例3的电解液。至此,制得实施例5的锂半电池。
实施例6
组2颗钮扣型半电池(尺寸CR2032),其中电池正极采用氧化锂钴(LiCoO2)(其中LiCoO2:超级导电碳黑:聚偏二氟乙烯粘着剂=94:3:3(重量比)),负极采用锂金属,隔离膜采用聚丙烯/聚乙烯/聚丙烯(PP/PE/PP)三层膜(商品名Celgard2325),且电解液组成采用实施例4的电解液。至此,制得实施例6的锂半电池。
比较例2
组2颗钮扣型电池(尺寸CR2032),其中电池正极采用氧化锂钴(LiCoO2)(其中LiCoO2:超级导电碳黑:聚偏二氟乙烯粘着剂=94:3:3(重量比)),负极为锂金属,隔离膜为PP/PE/PP三层膜(商品名Celgard2325)电解液组成采用比较例1的电解液。至此,制得比较例2的锂半电池。
将实施例5、实施例6、比较例2的锂半电池进行分解电压测试。线性扫描伏安法(linear sweep voltammetry,LSV)是通过连续测试通过一个电池或电极的电流,并加以记录电位随时间变化的方法。此处,以扫描率0.5mv/s于3V到6V之间使用AUTOLAB测量电解液的分解电压。
此外,以6C/30V条件进行高电压过充测试,利用扫描式电子显微镜附加能量分散光谱仪(Scanning Electron Microscope/Energy Dispersive Spectrometer;SEM/EDS)观察并分析正极表面的元素及其含量。
SEM/EDS检析结果显示:进行高电压过充试验前,无论有无含有机锂超分歧结构材料添加剂的锂金属氧化物正极材料,在未抽出锂离子前,氧元素与金属元素总量(不含锂元素)的比率约为4(其为六个测试区域点的平均值)。经过6C/30V条件的高电压过充测试后(抽出锂离子),未含有机锂超分歧结构材料添加剂的锂金属氧化物正极材料,其氧元素与金属元素总量(不含锂元素)的比率则从原来的4减降至1.8,显示氧的相对释出量超过50%。反观添加含有机锂超分歧结构材料的添加剂的锂金属氧化物正极材料,其氧元素与金属元素总量(不含锂元素)的比率则仅从原来的4减降至3.7(添加剂含量为0.5wt%时),氧的相对释出量低于10%,甚至氧元素与金属元素总量(不含锂元素)的比率与4相当(添加剂含量为2wt%时),氧的相对释出量低于5%。
锂金属氧化物正极材料中的氧如释放过多时,将会使结构易于崩解,而造成不可逆率增加及电池性能大幅减降的现象,也是导致电池因热失控(thermalrun-away)而会产生燃烧爆炸的关键要因;如能够有效减降氧的释出量,除可保持原有结构体系外,亦可降低电池因热失控而产生燃烧爆炸的风险,提升电池的安全性能。由SEM/EDS检析可知,金属氧化物中的氧相对释出量可从原本的超过50%大幅降至低于5~10%。
表2
如表2的实施例5及实施例6结果显示,添加了本发明的电解液添加剂后,电解液的分解电压可高达5.5V,且可提升电解液热耐受温度达至少10℃,能大幅增进电池的安全性,这是因为本发明的这一含有机锂的超分歧高分子结构材料添加剂对电解液具良好的溶合性,充电后于正负极表面可形成数纳米厚度的固态电解质界面(solid electrolyte interface,SEI)膜,所述SEI膜呈现出优异的结构强度与韧性。此外,含有机锂的超分歧高分子结构材料添加剂亦能减降对锂离子的溶剂效应并维系及稳定电解液的化学稳定性,亦可形成类离子液体通道。此外,添加于锂离子二次电池用电解液中,于充电达到一定电压时,添加剂可与正负极材料形成优质具结构韧性的SEI膜保护电极材料,并避免电极内的锂释出结合至SEI膜中,能减降不可逆率,增长电池的高低温循环寿命,且建构场效作动安全防护结构网,提高电池的耐热与耐过充性能。
综上所述,含有机锂的超分歧结构材料添加剂能够藉由本身对锂盐及有机溶剂系统的场效配位作用,强化及维系电解液相关组成的动态平衡体系,增益电解液的电化学与耐热稳定度,并使电池的充放电效能和电解液的稳态缓冲机制性能更加提升。此外,当电池电压超过添加剂电聚合的电压时,添加剂内的电致聚合超分歧结构材料,会再启动聚合作用,并于电极表面形成钝化层,使电池的内阻迅速上升,可减缓或阻止电解液进一步的分解,达到阻断热失控效果并保持电池及电解液处于安全状态。
虽然本发明已以实施例揭露如上,然其并非用以限定本发明,任何所属技术领域中具有通常知识者,在不脱离本发明的精神和范围内,当可作些许的更动与润饰,故本发明的保护范围当视后附的权利要求书所界定的范围为准。
Claims (22)
1.一种锂离子二次电池用的电解液添加剂,包括:
含氮的有机锂化合物;以及
超分歧结构材料。
2.如权利要求1所述的锂离子二次电池用的电解液添加剂,其中所述含氮的有机锂化合物,锂元素接在氮元素上。
3.如权利要求1所述的锂离子二次电池用的电解液添加剂,其中所述含氮的有机锂化合物还包括硅、硫、氧中的至少的一个元素。
6.如权利要求1所述的锂离子二次电池用的电解液添加剂,其中所述超分歧结构材料为含氮的超分歧高分子。
7.如权利要求1所述的锂离子二次电池用的电解液添加剂,其中所述超分歧结构材料的单体选自由马来酰亚胺、双马来酰亚胺、多马来酰亚胺、巴比土酸、咪唑、吡咯、吡啶、哒嗪、嘧啶、吡嗪、三嗪及其衍生物所组成的群组中的至少一种。
8.如权利要求1所述的锂离子二次电池用的电解液添加剂,其中所述含氮的有机锂化合物与所述超分歧结构材料的重量比为1:99~99:1。
9.如权利要求1所述的锂离子二次电池用的电解液添加剂,其中所述电解液添加剂占电解液总重的0.1wt%至10wt%。
10.一种锂离子二次电池,包括:
正极;
负极;
隔离膜;
电解液;以及
电解液添加剂,包括含氮的有机锂化合物以及超分歧结构材料。
11.如权利要求10所述的锂离子二次电池,其中所述含氮的有机锂化合物,锂元素接在氮元素上。
12.如权利要求10所述的锂离子二次电池,其中所述含氮的有机锂化合物还包括硅、硫、氧中的至少的一个元素。
15.如权利要求10所述的锂离子二次电池,其中所述超分歧结构材料为含氮的超分歧高分子。
16.如权利要求10所述的锂离子二次电池,其中所述含氮的有机锂化合物与所述超分歧结构材料的重量比为1:99~99:1。
17.如权利要求10所述的锂离子二次电池,其中所述电解液添加剂占所述电解液总重的0.1wt%至10wt%。
18.如权利要求10所述的锂离子二次电池,其中所述负极包括负极活性物,所述负极活性物是选自由介稳相球状碳、气相成长碳纤维、纳米碳管、焦炭、碳黑、石墨、乙炔黑、碳纤维、玻璃质碳、锂合金及其混合物所组成的族群。
19.如权利要求10所述的锂离子二次电池,其中所述负极还包括负极粘合剂,所述负极粘合剂为聚偏二氟乙烯、铁氟龙、苯乙烯丁二烯橡胶、聚酰胺树脂、三聚氰胺树脂或羧甲基纤维素粘合剂。
20.如权利要求10所述的锂离子二次电池,其中所述正极包括正极活性物,所述正极活性物是选自由钒、钛、铬、铜、钼、铌、铁、镍、钴及锰的锂化氧化物、锂化硫化物、锂化硒化物、锂化碲化物及其混合物所组成的族群。
21.如权利要求10的所述高分子锂离子二次电池,其中所述正极还包括正极粘合剂,所述正极粘合剂为聚偏二氟乙烯、铁氟龙、苯乙烯丁二烯橡胶、聚酰胺树脂、三聚氰胺树脂、羧甲基纤维素粘合剂。
22.如权利要求10所述的锂离子二次电池,其中所述正极还包括导电性添加物,所述导电性添加物选自由乙炔黑、碳黑、石墨、镍粉、铝粉、钛粉及不锈钢粉及其混合物所组成的族群。
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