CN104638239B - 具有核‑壳结构的材料 - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000011258 core-shell material Substances 0.000 title description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052718 tin Inorganic materials 0.000 claims abstract description 43
- 239000011246 composite particle Substances 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 239000011135 tin Substances 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 6
- 239000000956 alloy Substances 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004411 aluminium Substances 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002059 quaternary alloy Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 229910002058 ternary alloy Inorganic materials 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000005864 Sulphur Substances 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000443 aerosol Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000006911 nucleation Effects 0.000 claims description 4
- 238000010899 nucleation Methods 0.000 claims description 4
- 238000009825 accumulation Methods 0.000 claims 3
- 239000011230 binding agent Substances 0.000 claims 2
- 239000011162 core material Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 6
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 3
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011533 mixed conductor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KDWIPXPMLJALRS-UHFFFAOYSA-N [Sn].c1ccc2cc3ccccc3cc2c1 Chemical compound [Sn].c1ccc2cc3ccccc3cc2c1 KDWIPXPMLJALRS-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- -1 carbide Chemical compound 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
公开了一种具有复合颗粒的材料。该复合颗粒包括外壳和内核,所述外壳含有如碳、氮、氧和硫的元素,所述内核由锂合金化材料如锡、硅、铝和/或锗制成。如果外壳由碳制成,则复合颗粒的外壳具有小于20nm的平均厚度,且复合颗粒具有小于100nm的外部平均直径。在一些情形中,内核由锡、锡二元合金、锡三元合金和锡四元合金制成。
Description
本申请是申请日为2009年4月16日、发明名称为“具有核-壳结构的材料”的中国专利申请200910134292.7的分案申请。
政府权利
本发明是在由美国能源部签署的No.DE-AC52-06NA25396合同利用美国政府的支持而完成的。在本发明中,美国政府具有一定的权利。
技术领域
本发明涉及一种材料,特别是具有核-壳结构的材料。
背景技术
对电池的能量要求持续增长,而在体积和质量方面的限制却持续存在。此外,对安全、低成本和环境友好材料的需求也在增长。使用常规锂离子电池化学物质不能满足这些需求和电池的技术要求。尽管锂离子电池已经得到优化且显示了稳定的能量,这些系统受到了锂的量的限制,所述锂可以可逆地嵌入电池的活性材料结构中和从其中移出。
对于更高性能、安全、低成本和环境友好材料的需求只能通过开发新的电池材料来实现。研究人员已提出了用锡取代碳基阳极。在电池的充电期间,锡与锂合金化。锂锡合金形成了每1个锡原子4.4个锂原子的最大浓度,该浓度相当于993mAh/g的容量。常规碳基阳极具有372mAh/g的理论容量。因此,用锡基阳极电池取代常规碳基阳极电池能够产生更高的能量容量。
研究显示,使用锡基阳极存在两个主要问题。第一为差的循环寿命,而第二为差的锡利用率。差的循环寿命定义为作为充电-放电循环次数的函数的不良的电池能量保持率。研究人员已采用两种方法解决这些问题。首先,通过形成锡和至少一种其它金属的金属间化合物,其次,通过向阳极复合物添加非电化学活性材料。然而,现有的研究不能解决锂锡电池的不良性能的基本原因,所述原因为:1)充电时锂与锡的合金化所产生的锡锂颗粒的大的体积膨胀;及2)在上述体积膨胀期间锡团聚物的破碎。体积膨胀在后续循环期间导致了锡颗粒从基质中分离,而锡团聚物的破碎导致具有暴露的新表面区域的细颗粒。该新表面区域与基质不接触,因此如锡颗粒从基质中分离一样,导致了电池容量的降低。因此,需要具有足够循环寿命和适当的锡利用率的锂锡电池。
发明内容
所公开的是具有复合颗粒的材料。该复合颗粒包括含有例如碳、氮、氧或硫元素的外壳和由锂合金化材料如锡、硅、铝和/或锗制成的内核。如果外壳由碳制成,则复合颗粒的外壳具有小于20nm的平均厚度,且复合颗粒具有小于100nm的外部平均直径。在一些情形中,内核由锡、锡二元合金、锡三元合金或锡四元合金制成。
附图说明
图1是依据本发明实施方案的材料的截面示意图;
图2是用于本发明实施方案的制备方法的流程图;
图3是具有锡核的碳外壳的透射电子显微图像。
具体实施方式
本发明包括由复合颗粒制成的材料,所述复合颗粒具有外壳和内核。该内核由锂合金化材料制成,而外壳是电子导体、离子导体和/或混合导体。在电池工作期间,壳可以与锂可逆地反应或者可以不与锂可逆地反应,以提供额外的能量。应理解,如果壳与锂可逆地反应,则其能够通过抑制锂在阳极表面的镀覆而在过充电方面提供安全缓冲。因此,该材料可用于电化学装置。
在一些情形中,在使用该材料期间,核是实心的。例如,内核可以由锂合金化材料制成,示例性地包括锡、二元锡合金、三元锡合金等。应理解,可组合多个复合颗粒以制备电极,该电极是电化学装置的一部分。
还公开了制备复合颗粒的方法。该方法包括提供具有外壳和内核成分(component)的前体粉末。在气体中悬浮该前体材料粉末以形成气溶胶,然后使气溶胶通过等离子炬的热区。使前体粉末通过等离子炬会产生核-壳复合颗粒,其中核通常占据外壳内部容积的100%。
现在转向图1,以标记10总体表示由依据本发明实施方案的复合颗粒制成的材料。材料10包括复合颗粒100,该颗粒100具有外壳110和内核120。应理解,内核120可以包括2个独立容积,芯核材料的第一容积和孔隙空间的第二容积。在替代方案中,内核120可以仅包括芯核材料的一个容积。
内核120可以由锂合金化材料制成,示例性地包括锡、硅、铝、锗、及其组合和合金。外壳110还可以由各种材料制成。例如,如氧化物、碳酸盐、卤化物、碳化物、石墨、石墨烯(graphene)、蒽和无定形碳的材料可用于形成复合颗粒的外壳,只要所获的外壳是电子导体、离子导体和/或混合导体即可。
复合颗粒100的外部平均直径小于1000nm,在一些情形中可以小于500nm,或者在替代方案中小于100nm。如果外壳110由碳制成,则外部直径小于100nm。在其它情形中,复合颗粒100的外部平均直径小于70nm,而在另外情形中,外部平均直径小于50nm。外壳110的平均壁厚小于200nm,在一些情形中,可以小于100nm,或者在替代方案中,小于20nm。如果外壳110由碳制成,则外部直径小于20nm。
在图2中示例性地显示了制备本文公开的材料的方法。该方法包括在步骤200中提供含有所述材料的前体粉末,所述材料至少部分构成外壳和内核,且在步骤210中使前体粉末通过等离子炬。在步骤210中使前体粉末通过等离子炬时,在步骤220中制备核-壳粉末,例如图1所示的多个复合颗粒100。如果需要这样,可以在步骤230中由在步骤220中制备的复合颗粒制成电极。应理解,可以这样制备复合颗粒100,使得内核120是预锂化(prelithiated)的锂合金化材料,即内核120由在形成复合颗粒100时已经与锂合金化的材料制成。
为了更好理解上述实施方案,提供了复合颗粒及其制备方法的实施例。
实施例
为制备碳壳-锡核复合颗粒,制备了锡与蒽比为50:1的干燥的前体粉末。应理解,其它芳族焦炭形成化合物如萘或苊(acenaphthalene)可用于提供碳材料。在氩气中悬浮前体粉末,由此制备具有蒽和锡的氩气气溶胶气体。使该气溶胶气体穿过具有集中于耦合器中的微波能量的低功率大气压或近大气压等离子。应理解,还可以使用其它方法产生的等离子。除了气溶胶气体,使二次供给的氩气穿过等离子区域。
不受理论束缚,本发明人认为穿过等离子热区时,前体粉末中的碳经历了形成碳碎片的碳化机制。此外,前体粉末中的锡熔化并当冷却时通过成核过程形成颗粒。碳碎片聚集于相同的核(锡)上,并基于相对混溶性偏析到核的表面。成核颗粒从热区离开进入余辉区,在该区中不发生进一步的生长。
图3显示了透射电子显微图像,其中使用蒽锡前体粉末制备了具有碳外壳和锡核的复合颗粒,氩气气溶胶气流流量为300立方厘米每分钟(cc/min),氩等离子气流流量为200cc/min,且发送的微波功率为900瓦。如该图所示,采用碳外壳和锡核制备了外部平均直径为50-100nm的复合颗粒。在该方法的这一步骤,锡核基本占据了碳外壳中的所有内部容积。
应理解,以上给出的实施例仅用于说明目的,本发明还包括其它制备具有外壳和核的复合颗粒的方法,所述核具有减小的尺寸,使得核可以在外壳中发生膨胀而所述外壳不破坏。
以上的附图、讨论和描述是对本发明特定实施方案的说明,但其并不意在对本发明的实施的限制。鉴于本文给出的教导,对本领域技术人员来说,本发明的多种修改和变体是显而易见的。在以下权利要求书(包括所有等价物)中界定了本发明的范围。
Claims (13)
1.一种材料,包含:
具有外壳和内核的复合颗粒,所述外壳由碳制成,所述内核具有第一容积和任选的第二容积,所述第一容积由锂合金化材料制成,所述锂合金化材料含有选自锡、硅、铝和锗的元素,所述任选的第二容积是孔隙空间;
所述复合颗粒具有小于100nm的外部平均直径;
其中所述外壳具有小于20nm的平均厚度;
且其中所述锂合金化材料选自锡、锡二元合金、锡三元合金和锡四元合金,
其中所述复合颗粒是通过包括如下步骤的方法制备的:
提供具有外壳和内核的成分的粉末前体材料;
在氩气气体中悬浮该前体材料的所述粉末以形成气溶胶;和
使气溶胶穿过等离子炬的热区,其中所述前体材料中的碳经历形成碳碎片的碳化机制;
使所述前体粉末中锡材料熔化以当冷却时通过成核过程形成核;和
使所述碳碎片聚集于所述核上,并基于相对混溶性偏析到核的表面。
2.权利要求1的材料,其中所述复合颗粒具有小于70nm的外部平均直径。
3.权利要求1的材料,其中所述复合颗粒具有小于50nm的外部平均直径。
4.用于锂电池的阳极,所述阳极包含:
具有外壳和内核的复合颗粒,所述外壳由碳制成,所述内核具有第一容积和任选的第二容积,所述第一容积由锂合金化材料制成,所述锂合金化材料含有锡,所述任选的第二容积是孔隙空间;
所述复合颗粒具有小于100nm的外部平均直径;
其中所述复合颗粒的所述外壳具有小于20nm的平均厚度;
其中所述锂合金化材料选自锡、锡二元合金、锡三元合金和锡四元合金,
其中所述复合颗粒是通过包括如下步骤的方法制备的:
提供具有外壳和内核的成分的粉末前体材料;
在氩气气体中悬浮该前体材料的所述粉末以形成气溶胶;和
使气溶胶穿过等离子炬的热区,其中所述前体材料中的碳经历形成碳碎片的碳化机制;
使所述前体粉末中的锡熔化以当冷却时通过成核过程形成核;和
使所述碳碎片聚集于所述核上,并基于相对混溶性偏析到核的表面。
5.权利要求4的阳极,其中所述复合颗粒具有小于70nm的外部平均直径。
6.权利要求5的阳极,其中所述复合颗粒具有小于50nm的外部平均直径。
7.权利要求4的阳极,还包含粘结剂。
8.用于锂电池的阳极,所述阳极包含:
具有外壳和内核的复合颗粒,所述外壳含有选自碳、氮、氧和硫的元素,所述内核具有第一容积和任选的第二容积,所述第一容积由锂合金化材料制成,所述锂合金化材料含有选自锡、硅、铝和锗的元素,所述第二容积是孔隙空间;
所述复合颗粒具有小于100nm的外部平均直径,且所述外壳具有小于20nm的平均厚度,
其中所述复合颗粒是通过包括如下步骤的方法制备的:
提供具有外壳和内核的成分的粉末前体材料;
在氩气气体中悬浮该前体材料的所述粉末以形成气溶胶;和
使气溶胶穿过等离子炬的热区,其中所述前体材料中的碳经历形成碳碎片的碳化机制;
使所述前体粉末中的锡材料熔化以当冷却时通过成核过程形成核;和
使所述碳碎片聚集于所述核上,并基于相对混溶性偏析到核的表面。
9.权利要求8的阳极,其中所述复合颗粒具有小于70nm的外部平均直径。
10.权利要求9的阳极,其中所述复合颗粒具有小于50nm的外部平均直径。
11.权利要求8的阳极,其中所述外壳是碳。
12.权利要求8的阳极,其中所述内核由锂合金化材料制成,所述锂合金化材料选自锡、锡二元合金、锡三元合金和锡四元合金。
13.权利要求8的阳极,还包含粘结剂。
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US9558860B2 (en) * | 2010-09-10 | 2017-01-31 | Samsung Electronics Co., Ltd. | Graphene-enhanced anode particulates for lithium ion batteries |
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