CN113206257B - 一次锂电池及其制备方法 - Google Patents
一次锂电池及其制备方法 Download PDFInfo
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- CN113206257B CN113206257B CN202110445389.0A CN202110445389A CN113206257B CN 113206257 B CN113206257 B CN 113206257B CN 202110445389 A CN202110445389 A CN 202110445389A CN 113206257 B CN113206257 B CN 113206257B
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- lithium
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- lithium battery
- metal
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 143
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 67
- 239000002184 metal Substances 0.000 claims abstract description 67
- 239000010409 thin film Substances 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 230000000149 penetrating effect Effects 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 19
- -1 polyethylene Polymers 0.000 claims description 15
- 239000010408 film Substances 0.000 claims description 13
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 229910000733 Li alloy Inorganic materials 0.000 claims description 8
- 239000001989 lithium alloy Substances 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 239000007784 solid electrolyte Substances 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 6
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 claims description 3
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
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- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
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- 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
- 229910052802 copper Inorganic materials 0.000 claims description 2
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- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
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- 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 description 2
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
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- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
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- 238000009941 weaving Methods 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- YBDACTXVEXNYOU-UHFFFAOYSA-N C(F)(F)(F)F.[Li] Chemical compound C(F)(F)(F)F.[Li] YBDACTXVEXNYOU-UHFFFAOYSA-N 0.000 claims 1
- GPVWCGHDIGTNCE-UHFFFAOYSA-N [Fe](=S)=S.[Li] Chemical compound [Fe](=S)=S.[Li] GPVWCGHDIGTNCE-UHFFFAOYSA-N 0.000 claims 1
- SOZVEOGRIFZGRO-UHFFFAOYSA-N [Li].ClS(Cl)=O Chemical compound [Li].ClS(Cl)=O SOZVEOGRIFZGRO-UHFFFAOYSA-N 0.000 claims 1
- GJCNZQUZWSHFHP-UHFFFAOYSA-N [Li].O=S=O Chemical compound [Li].O=S=O GJCNZQUZWSHFHP-UHFFFAOYSA-N 0.000 claims 1
- FBDMJGHBCPNRGF-UHFFFAOYSA-M [OH-].[Li+].[O-2].[Mn+2] Chemical compound [OH-].[Li+].[O-2].[Mn+2] FBDMJGHBCPNRGF-UHFFFAOYSA-M 0.000 claims 1
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- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
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- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- 241001391944 Commicarpus scandens Species 0.000 description 1
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- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
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- 229910000502 Li-aluminosilicate Inorganic materials 0.000 description 1
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- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
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Abstract
公开了一种一次锂电池及其制备方法。本发明的一次锂电池的负极是超轻三维骨架金属锂复合体,其具有:不导电的高分子聚合物三维骨架;沉积在三维骨架内部的、用于提高金属锂浸润性的纳米功能粒子;分布于三维骨架表面且贯穿三维骨架内部的金属锂薄膜,其中,借助于提高金属锂浸润性的纳米功能粒子,金属锂薄膜形成贯穿三维骨架的导电通道;和任选地,位于金属锂薄膜外表面的表面保护层。该负极克服了传统的锂带负极抗拉强度低、使用厚锂带降低比能量及锂资源浪费的问题。
Description
技术领域
本发明涉及储能技术领域,特别涉及一次锂电池及其制备方法。
背景技术
一次锂电池具有比能量高,电压高,自放电小,工作温度范围广的优点,被广泛应用于照相机、智能仪表、水表、电表、气表、石油勘探、医疗器械、防盗报警等领域。金属锂的原子质量小,电化学电位最负,与氧亚硫酰氯、二氧化锰等正极材料以及非水电解质组成的电池的比能量很高。目前一次锂电池的负极大部分是采用的厚金属锂带,锂带厚度≥1mm,但实际利用的金属锂厚度没有那么厚,会有部分的金属锂剩余不参与反应,造成金属锂资源的浪费。而金属锂带本身比较柔软,抗拉强度低(约1.156MPa),当采用厚度≤0.1mm金属锂带做一次电池的负极时,需要使用金属箔材例如铜箔、不锈钢箔材等做金属锂带的支撑基材,才能更好的收放卷使用。但金属箔材一般都很重,降低电池的比能量。
发明内容
本发明主要目的在于提供一种一次锂电池及其制备方法,其可以解决一次锂电池中使用纯锂带抗拉伸强度低的问题。
本发明采用如下技术方案:
在一些实施例中提供一种一次锂电池,所述的锂电池负极是超轻三维骨架金属锂复合体,所述复合体具有:不导电的高分子聚合物三维骨架;沉积在三维骨架内部的、用于提高金属锂浸润性的纳米功能粒子;分布于三维骨架表面且贯穿三维骨架内部的金属锂薄膜,其中,借助于提高金属锂浸润性的纳米功能粒子,金属锂薄膜形成贯穿三维骨架的导电通道;和任选地,位于金属锂薄膜外表面的表面保护层,其中,所述超轻三维骨架金属锂复合体具有1.0-200微米的均匀厚度,厚度公差在±0.5μm以内,所述超轻三维骨架金属锂复合体的密度小于等于单纯金属锂薄膜的密度。
根据本发明的实施例,金属锂贯穿于骨架材料内部和表面,金属锂本身能传导电子,有利于电池反应时均匀集流和散热;由于骨架材料密度小,质量轻,有利于提高电池的比能量。
在一些实施例中提供一种制备上述一次锂电池的方法,所述方法包括:通过模切机将成卷的超轻三维骨架金属锂复合体冲片成一定尺寸的片作为负极;将所述负极片与电解液、隔膜和正极一起组成一次锂电池,或者将所述负极片与固态电解质和正极一起组成一次锂电池。
本发明可以具有以下有益效果中的至少一种:
(1)超轻三维骨架金属锂复合体密度小,质量轻,实现电池的高能量密度。
(2)金属锂贯穿于骨架材料内部和表面,一方面提高了金属锂层的抗拉强度,另一方面也有利于电池反应时均匀集流和散热。
(3)超轻三维骨架金属锂复合体抗拉强度大(≥30MPa),可以成卷收放卷使用,有利于产业化连续生产。
附图说明
图1为根据本发明实施例1获得的超轻三维骨架金属锂复合体(尼龙锂带产品)的实物图。
具体实施方式
本发明一方面提供了一种一次锂电池,其负极由具有纳米功能粒子的超轻骨架材料和金属锂或锂合金及任选的表面保护层(例如人工SEI膜)组成。
其中,超轻骨架材料可以为聚合物:例如聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、丁苯橡胶、顺丁橡胶、异戊橡胶、乙丙橡胶、酚醛树脂、环氧树脂、不饱和聚酯树脂、粘胶纤维、醋酸纤维、尼龙、涤纶、聚甲醛、聚碳酸酯、聚酰胺、聚酰亚胺、聚芳醚、聚芳酰胺中的一种或者多种组合。所述超轻骨架材料经过静电纺丝或者编制而形成三维骨架结构。
本申请的发明人出人意料地发现:通过在骨架材料中导入用于提高金属锂浸润性的纳米功能粒子,可以有效改善骨架材料与金属锂的浸润性,使得熔融的金属锂可以有效进入骨架材料的内部空间,金属锂贯穿于骨架材料内部和表面。这样不仅解决了金属锂带抗拉强度低的问题,而且还可以直接应用于金属锂电池,有利于电池反应时均匀集流和散热。
可用于本发明的纳米功能粒子可以包括:
半导体(磷化铟(InP)、硅(Si)、氮化镓(GaN)、氮化硼(BN))纳米粒子、含亲锂基团的有机纳米粒子中的一种或多种,所述亲锂基团包括氨基、硝基、吡咯、吡啶、咪唑、氟、胺类、腈类、叠氮、偶氮、重氮基团中的至少一种。含亲锂基团的有机纳米粒子优选为亲锂有机聚合物(聚偏氟乙烯PVDF、聚乙烯吡咯烷酮PVP)纳米粒子中的一种或多种。可选地,纳米功能粒子与三维骨架的质量比在1%至15%范围内。
优选地,纳米功能粒子通过热蒸镀或者气相沉积进入三维骨架内部。
本发明中,超轻三维骨架金属锂复合体可以为厚度均匀的带材,其中金属锂薄膜具有完整的薄膜形状(没有明显的褶皱和变形,有齐整的边缘)。优选地,金属锂薄膜形成于三维骨架的两侧表面,且两侧表面上的金属锂薄膜均具有完整的薄膜形状。
可选地,超轻三维骨架金属锂复合体的锂膜表面具有金属光泽,超轻三维骨架金属锂复合体的厚度范围为1.0-200微米,优选1-50微米,更优选30微米以下,厚度公差为±0.5μm,优选±0.1μm。
可选地,金属锂薄膜的材料包括纯金属锂或者锂合金。纯金属锂膜主体的锂元素含量可以为99.95%-99.99%。锂合金为金属锂与硅、镁、铝、铟、硼、锡、镓、钇、银、铜、铅、铋、钠、碳、锗、钛、铬、钴、钨、铁、铌、镍、金、钡、镉、铯、钙、锰、氮、铂、硫、铊、锶、碲、锌、锑、锆中一种或多种的合金;其中锂含量为5%-99.9%。优选地,所述金属锂薄膜通过向内部沉积有纳米功能粒子的三维骨架喷淋熔融金属锂或锂合金而形成。
可选地,由于金属锂比较活泼,容易与空气中的氧气、氮气、二氧化碳等反应,降低了金属锂的活性,本发明可以对金属锂进行表面修饰,以解决金属锂的贮存问题,有利于金属锂应用于金属锂电池。
可选地,表面保护层的厚度为5纳米~100微米。可以通过在金属锂薄膜表面喷涂、浸涂、气相沉积有机试剂(聚环氧乙烷PEO、聚乙烯醇、油酸、十八烷基磷酸、氟代碳酸乙烯酯FEC的一种或者多种组合)或者气体等离子刻蚀(二氧化碳、氮气、氟气、氧气中的一种或者多种组合),形成所述表面保护层,
优选地,所述表面保护层为固体电解质界面膜(SEI膜),厚度为5纳米~20微米。
上述的超轻三维骨架金属锂复合体可以通过以下方法制备,所述方法包括:
提供由不导电的高分子聚合物经过静电纺丝或者编制而成的三维骨架,并且通过热蒸镀或者气相沉积法,将用于提高金属锂浸润性的纳米功能粒子沉积在三维骨架内部,形成超轻三维骨架材料;
向所述超轻三维骨架材料连续或间断喷淋熔融金属锂或锂合金;
使喷淋后的材料通过设置有刮刀的出口,形成具有1.0-200微米的均匀厚度,厚度公差在±0.5μm以内的超轻三维骨架金属锂复合体。
可选地,所述方法还包括通过在金属锂薄膜表面喷涂、浸涂、气相沉积有机试剂或者进行气体等离子刻蚀,形成表面保护层。
可选地,所述方法是卷对卷的连续生产方法,包括使超轻三维骨架材料连续通过熔融金属锂喷涂池。
可选地,熔融池的温度范围是200~500℃,优选350~450℃。
可选地,环境气氛要求:整个超轻三维骨架金属锂复合体的制备在惰性气氛(例如氩气气氛)中进行,控制水含量小于0.1ppm,氧含量小于0.1ppm。
在一些实施例中,一次锂电池正极活性物质包括二氧化锰、氧亚硫酰氯、二硫化铁、氟化碳、二氧化硫、硫酰氯等。
可以选择的相匹配的电解液如下:亚硫酰氯(电解液:LiAlCl4、SOCl2);硫酰氯(电解液:LiAlCl4、SO2Cl2);二氧化硫(电解液:溴化锂、乙腈);
对于其它正极材料(二氧化锰、氟化碳、二硫化铁),可选择电解液为锂盐和溶剂的组合;其中锂盐包括:LiPF6(六氟磷酸锂)、LiClO4(高氯酸锂)、LiAlCl4(高铝酸锂)、LiBr(溴化锂)、LiI(碘化锂)、LiTFSI(双三氟甲基磺酰亚胺锂或称二(三氟甲基磺酸)亚胺锂);溶剂可以包括:乙腈、甲酸甲酯、碳酸丙烯酯、γ-丁内酯、二甲基亚砜、亚硫酸二甲酯、1,2-二甲基乙烷和四氢呋喃。
对于一次锂电池,电解质还可以选择固态电解质,例如:LiPON、氧化物固态电解质(锂磷氧氮化合物)、硫化物固态电解质(锂硫磷化合物)、(反)钙钛矿型、石榴石结构(锂镧锆氧化合物)和/或聚合物固态电解质(聚环氧乙烷、聚偏氟乙烯、聚丙烯酸酯、聚碳酸乙烯酯、聚甲基丙烯酸、聚丙烯腈)。
在一些实施例中,隔膜可以为聚丙烯/聚乙烯(PP/PE),可以使用带陶瓷涂层或聚合物涂层的隔膜,隔膜厚度:10-40微米。
电池形状选自下列各项中的一种:扣式电池,圆柱形电池,软包电池。
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。此外,下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1:
金属锂在熔融池内加热300℃,变成熔融锂,采用20微米聚酰亚胺薄膜PIP(江西先材纳米科技有限公司)为骨架材料,沉积PVP-K15(阿拉丁),两者质量比1%,喷淋涂布熔融锂金属锂得到锂膜产品,控制刮刀60微米,得到厚度为60微米(厚度公差为±0.5微米)的超轻三维骨架金属锂复合体产品(尼龙锂带)。图1为尼龙锂带产品的实物图。
实施例2:
使用实施1中超轻三维骨架金属锂复合体为一次锂电池的负极;正极活性物质选用二氧化锰材料,按照质量比二氧化锰(国药集团化学试剂有限公司):乙炔黑(阿法埃莎):聚四氟乙烯(深圳市科晶智达科技有限公司)=85:5:10称取各物质,加入N-甲基吡咯烷酮中(上海阿拉丁生化科技股份有限公司),固体和液体比例为180mg:1mL,混浆过夜(大于12小时)。将上述浆料通过涂布机涂布在铝箔表面,双面刮涂厚度为220微米,120℃真空干燥12h。在干燥车间(露点-45℃)将成卷的正极、负极通过机械化设备(借助放卷设备)冲成圆片作为正极、负极极片。电池采用CR2450型扣式电池,电解液为1M LiClO4,PC(LiClO4高氯酸锂,PC碳酸丙烯酯,苏州乾民化学试剂有限公司),隔膜为PP隔膜,充放电电压区间为3.2–2V,恒流充放电电流为0.5mA。
对比例1:
使用厚度为1mm金属锂带为一次电池负极,正极材料、隔膜、电解液及电池组装和实施例2一致。使用厚度1000微米金属锂带为负极时,借助放卷设备冲切负极片时,1000微米厚锂带未出现拉伸变形,也未拉扯断。
对比例2:
使用厚度为60微米金属锂带为一次电池负极,正极材料、隔膜、电解液及电池组装和实施例2一致。使用厚度60微米金属锂带为负极时,借助放卷设备冲切负极片时,60微米锂带放卷时容易断带,不能批量使用。
表1三种负极的比较
Claims (14)
1.一种一次锂电池,其特征在于:所述一次锂电池的负极是超轻三维骨架金属锂复合体,所述复合体具有:
不导电的高分子聚合物三维骨架,所述三维骨架由不导电的高分子聚合物经过静电纺丝或者编制而成,所述高分子聚合物包括:聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、丁苯橡胶、顺丁橡胶、异戊橡胶、乙丙橡胶、酚醛树脂、环氧树脂、不饱和聚酯树脂、粘胶纤维、醋酸纤维、尼龙、涤纶、聚甲醛、聚碳酸酯、聚酰胺、聚酰亚胺、聚芳醚、聚芳酰胺中的一种或者多种组合;
通过热蒸镀或者化学气相沉积进入三维骨架内部的、用于提高金属锂浸润性的纳米功能粒子,所述纳米功能粒子为聚偏氟乙烯纳米粒子、聚乙烯吡咯烷酮纳米粒子中的一种或多种;所述的纳米功能粒子与三维骨架的质量比在1%至15%范围内;和
分布于三维骨架表面且贯穿三维骨架内部的金属锂薄膜,其中,借助于提高金属锂浸润性的纳米功能粒子,金属锂薄膜形成贯穿三维骨架的导电通道;
其中,所述超轻三维骨架金属锂复合体具有1.0-200微米的均匀厚度,厚度公差在±0.5µm以内,所述超轻三维骨架金属锂复合体的密度小于等于单纯金属锂薄膜的密度。
2.根据权利要求1所述的一次锂电池,其特征在于:所述金属锂薄膜的材料包括纯金属锂或者锂合金,所述锂合金为金属锂与硅、镁、铝、铟、硼、锡、镓、钇、银、铜、铅、铋、钠、碳、锗、钛、铬、钴、钨、铁、铌、镍、金、钡、镉、铯、钙、锰、氮、铂、硫、铊、锶、碲、锌、锑、锆中一种或多种的合金。
3.根据权利要求2所述的一次锂电池,其特征在于:所述金属锂薄膜通过向内部沉积有纳米功能粒子的三维骨架喷淋熔融金属锂或锂合金而形成。
4.根据权利要求1所述的一次锂电池,其特征在于:所述一次锂电池的负极还包括位于金属锂薄膜外表面的表面保护层。
5.根据权利要求4所述的一次锂电池,其特征在于:所述表面保护层的厚度为5纳米~100微米。
6.根据权利要求4所述的一次锂电池,其特征在于:通过在金属锂薄膜表面喷涂、浸涂、气相沉积有机试剂或者气体等离子刻蚀,形成所述表面保护层。
7.根据权利要求6所述的一次锂电池,其特征在于:所述有机试剂为聚环氧乙烷、聚乙烯醇、油酸、十八烷基磷酸、氟代碳酸乙烯酯中的一种或者多种组合。
8.根据权利要求6所述的一次锂电池,其特征在于:所述气体等离子刻蚀采用二氧化碳、氮气、氟气、氧气中的一种或者多种组合。
9.根据权利要求4所述的一次锂电池,其特征在于:所述表面保护层为固体电解质界面膜,厚度为5纳米~20微米。
10.根据权利要求1所述的一次锂电池,其特征在于:所述一次锂电池包括锂-二氧化锰电池、锂-亚硫酰氯电池、锂-二硫化铁电池、锂-二氧化硫电池、锂-氟化碳电池。
11.根据权利要求1所述的一次锂电池,其特征在于:所述一次锂电池的形状包括圆柱式电池、软包电池、扣式电池。
12.根据权利要求1所述的一次锂电池,其特征在于:所述一次锂电池的正极活性物质包括二氧化锰、氧亚硫酰氯、二硫化铁、氟化碳、二氧化硫、硫酰氯中的至少一种。
13.根据权利要求1所述的一次锂电池,其特征在于:所述一次锂电池包括液体电解液或固态电解质。
14.一种制备根据权利要求1-13中任一项所述的一次锂电池的方法,其特征在于所述方法包括:
通过模切机将成卷的超轻三维骨架金属锂复合体冲片成一定尺寸的片作为负极;
将所述负极片与电解液、隔膜和正极一起组成一次锂电池,或者将所述负极片与固态电解质和正极一起组成一次锂电池。
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