CN116895730A - 用于可再充电锂电池的银掺杂的硫阴极材料 - Google Patents
用于可再充电锂电池的银掺杂的硫阴极材料 Download PDFInfo
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- CN116895730A CN116895730A CN202310247654.3A CN202310247654A CN116895730A CN 116895730 A CN116895730 A CN 116895730A CN 202310247654 A CN202310247654 A CN 202310247654A CN 116895730 A CN116895730 A CN 116895730A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000004332 silver Substances 0.000 title claims abstract description 48
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 47
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 42
- 239000011593 sulfur Substances 0.000 title claims abstract description 42
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 49
- 239000010406 cathode material Substances 0.000 title abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 5
- 229910052744 lithium Inorganic materials 0.000 title description 5
- 239000000463 material Substances 0.000 claims abstract description 31
- 229910052946 acanthite Inorganic materials 0.000 claims abstract description 21
- 229940056910 silver sulfide Drugs 0.000 claims abstract description 21
- 239000006182 cathode active material Substances 0.000 claims abstract description 20
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000011370 conductive nanoparticle Substances 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims 3
- 239000011149 active material Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000011530 conductive current collector Substances 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229940072107 ascorbate Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- NHCSMTQRYWPDDW-UHFFFAOYSA-N [C].[N].[S] Chemical compound [C].[N].[S] NHCSMTQRYWPDDW-UHFFFAOYSA-N 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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Abstract
将活性阴极材料用银掺杂以有效地改善所述阴极的电导率。所述活性材料可以是硫,并且所述银可以是银、硫化银或两者的形式。如果需要,所述阴极材料包括导电纳米颗粒的基质,所述导电纳米颗粒包括元素硫、银和/或硫化银。本公开也可应用于其他电池材料,例如磷酸铁锂。
Description
背景技术
需要有效、实用的储能装置。锂-硫二次(即,可再充电)电池已被考虑用于该目的。已知的锂-硫(Li-S)电池具有含有元素锂(Li)的阳极(负电极)、含有元素硫(S)的阴极(正电极)和位于阳极与阴极之间的电解质和隔膜。当二次电池被充电时,锂离子(Li+)从阴极向阳极迁移穿过电解质和隔膜。当电池放电时,锂离子沿相反方向即从阳极向阴极迁移穿过电解质和隔膜。
锂-硫电池的示例在美国专利第11,251,433号(2022年2月15日)(Nitrogen-sulfur-carbon nanocomposites and their application as cathode materials inlithium-sulfur batteries)、第11,239,465号(2022年2月1日)(Sulfur-carboncomposite,preparation method therefor,and lithium-sulfur battery comprisingsame)、第11,201,331号(2021年12月14日)(Positive electrode material for lithium-sulfur battery,preparation method therefor,and applications thereof)、第11,145,859号(2021年10月12日)(Metal oxide nanosheet-sulfur nanocomposite andlithium-sulfur battery using the same)和第11,075,400号(2021年7月27日)(Lithium-sulfur battery)中提及。
发明内容
本公开涉及用于二次电池的阴极的掺杂材料,其中阴极材料包含:活性阴极材料;和银,其中阴极中活性阴极材料的量大于阴极中银的量,但银有效地改善阴极的电导率。
根据本公开的一个方面,活性阴极材料包含硫,并且银呈银金属(Ag)和/或硫化银(Ag2S)的形式。如果需要,活性阴极材料包含元素硫,并且阴极材料包含导电纳米颗粒的基质,所述导电纳米颗粒包含元素硫、银和/或硫化银。银/硫化银可以改善阴极的电导率。
本公开还涉及一种二次电池,其中活性阴极材料形成含有金属银和/或银化合物的基质。
本公开还涉及制造用于二次电池的阴极材料的方法。
附图说明
图1是根据本公开构造的二次电池的示例的侧视图;
图2是图1所示的二次电池的俯视图;
图3是图1和图2所示的电池的沿图2的线3-3截取的示意性截面图;
图4是制造用于图1至图3所示电池的阴极的银掺杂的硫材料的方法的示例的工艺流程图;以及
图5是图1至图3中所示的电池的阴极的一部分的放大示意性截面图,该部分由图3的圆圈5表示。
在所有附图中,相同的元件由相同的附图标记和其他字符表示。这些附图示出了用于说明和解释本公开的非限制性示例,并且未必按比例绘制。
具体实施方式
现在参考附图,根据本公开构造的二次电池10(图1)的示例具有圆柱形外壳12、阴极侧导电集电器14(图2)和阳极侧导电集电器16(图3)。本公开不应受限于附图中所示和本文中提及的配置,除非在所附权利要求中叙述了此类特征。因此,例如,本公开不应受限于具有圆柱形外壳的装置。
在附图中以示例方式示出的外壳12可以由合适的、耐用的、非导电(电绝缘)材料制成。导电集电器14、16可以由一种或多种合适的导电材料制成,诸如不锈钢、铝、镍、铜、钛、铂、金、银、钌、钽、铌、铪、锆、钒、铟、钴、钨,锡、铍和钼。如果需要,阴极侧集电器14可包括合适的铝箔,而阳极侧集电器16可包括铜箔。然而,本公开不应受限于附图中所示和本文中提及的配置和材料,除非在所附权利要求中叙述了此类特征。
现在参考图3,所示电池10还具有阴极18、阳极20、电解质22和隔膜24。阴极18位于外壳12内并接触阴极侧导电集电器14。阴极18包含银掺杂的硫材料,该材料可以包含元素硫(S)(活性阴极材料的示例)和银(Ag)和/或硫化银(Ag2S),如下面更详细描述的那样。
阳极20也位于外壳12内,但接触阳极侧导电集电器16。阳极20包含一种或多种合适的活性阳极材料,诸如锂(Li)、天然和人造石墨、活性炭、炭黑、导电添加剂、钛酸锂(Li4Ti5O12或LTO)、表面官能化的硅和粉末状石墨烯。
电解质22可包括一种或多种合适的材料,诸如非水性液体电解质、离子液体、固体聚合物和玻璃-陶瓷电解质。如果需要,电解质22可以包括盐、溶剂和添加剂。一种或多种盐可以提供锂离子(Li+)23进出阴极18和阳极20的路径。溶剂可以包括一种或多种用于溶解盐的有机液体,并且添加剂可以针对特定的、期望的目的而少量使用。在所示示例中,电解质22优先地仅允许锂离子23(而不是任何电子)进出电池10内的电极18、20。
隔膜24是位于电池电极18、20之间的半渗透屏障。隔膜24可以防止电子穿过电池10传输,从而仅允许锂离子23穿过隔膜24内的内部微观开口。可根据期望的物理和电化学特性来选择隔膜24的配置和材料。隔膜24可以包括例如一种或多种合成树脂,诸如聚乙烯和聚丙烯。
在操作中,在电池充电过程期间,合适的充电器(图中未示出)电连接到导电集电器14、16,并使电子(e-)从阴极18穿过阴极侧集电器14、穿过位于电池10外部的一根或多根合适的导线(未示出)传导到阳极侧集电器16,然后传导到阳极20。同时,锂离子(Li+)23沿第一箭头25示意性指示的方向从阴极18穿过电解质22和隔膜24传输到阳极20。
在电池充电过程之后,可以通过将合适的负载(未示出)电连接到导电集电器14、16,并使电子从阳极20穿过阳极侧集电器16、穿过位于电池外壳12外部的一根或多根合适的导线(未示出)传导到阴极侧集电器14,然后传导到阴极18,来执行电池放电过程。在电池放电过程期间,锂离子23沿第二箭头26示意性指示的方向从阳极20穿过电解质22和隔膜24传输到阴极18。然后,电池充电和电池放电过程可以按交替的循环方式重复多次。
现在参考图4,制造用于阴极18的银掺杂的硫材料110的方法可以包括至少第一、第二和第三连续步骤100、112、114。在第一步骤100中,将胶体银溶液102中的少量元素银(Ag)加入并混合到合适的液体还原剂104中以形成银(Ag)胶体106。胶体银溶液的悬浮介质可以是合适的液体,例如水或酸性溶液。还原剂104可以是合适的液体,例如硼氢化钠、柠檬酸盐和抗坏血酸盐或金属粉末,诸如铁或锌粉。
然后,在步骤112中,将元素硫(S)108加入并混合到银胶体106中。一些硫108可与银胶体106中的银反应以形成硫化银(Ag2S)和/或以金属形式(Ag)掺杂。
然后,在步骤114中,允许或使银掺杂的硫材料110从步骤112中产生的混合物中沉淀出来。银掺杂的硫材料110包括已经用胶体银处理过的元素硫的基质。在硫基质内形成含有硫化银的导电纳米颗粒120(图5)。银掺杂的硫材料110的电导率远大于硫108的电导率,即使银掺杂的硫材料110仅含有非常少量的银。如果需要,银掺杂的硫材料110中银与硫的重量比可以小于或等于100:1,000,000。
银胶体106可通过任何合适的方法制备。根据本公开的一个方面,银胶体106可通过用还原剂如硼氢化钠、柠檬酸盐和抗坏血酸盐化学还原银盐来合成。
图3所示的阴极18可以全部或至少部分地由银掺杂的硫材料110形成。银掺杂的硫材料110是以下物质的基质:(A)可含有少量硫化银的导电纳米颗粒120,(B)较大量的元素硫,(C)和/或一些元素银,和(D)任选的一种或多种其他材料,包括例如添加剂和杂质。阴极18中硫的量远大于阴极18中硫化银的量。如果需要,阴极18中硫与银的重量比可以大于或等于1,000,000:100。
银掺杂的硫材料110有利地具有高电导率。选择硫作为二次电池的阴极活性材料有许多原因。这些原因包括高能量密度和相对低的硫成本。然而,硫的电导率极低。实际上,硫被认为是电绝缘体。碳(C)可以作为导电基质添加到硫中,以允许电子在阴极与阳极之间转移。然而,充分增加碳-硫(C-S)混合物的电导率所需的大量碳导致阴极厚度增加。随着阴极厚度增加,离子不能有效地扩散通过厚阴极而成为限速性的。
因此,在阴极18中具有所示的银掺杂的硫材料110的本文作为示例描述的电池10可提供改进的性能。阴极18的质量(尺寸)可保持较小(不因碳的存在而增加),同时保持阴极18的期望电导率。由于硫化银和银的高电导率,可以使用极少量的银来提供实现期望电子转移所需的电导率的巨大有利效果。
实际上,银是最导电的元素。此外,银可以与硫反应形成稳定的硫化银,并且在充电过程中不会从阴极18转移到阳极20。少量的银可足以将硫的电导率提高几个数量级。在阴极中实现期望电导率可能所需的银的量为百万分之几的量级,因此对电池10生产成本的影响极小,并且对阴极18的功能所需质量(尺寸)的影响也极小。
在许多情况下,不令人满意的电池性能是由于阴极活性材料的低电导率所致。尽管可以将导电材料如碳加入到硫中以提高阴极的电导率,但是阴极重量和厚度的相应增加是不利的。由于其高电导率,在活性阴极材料的基质内提供银/硫化银可以显著提高阴极材料的电导率,而不会不利地影响阴极的厚度。与碳不同,向用于阴极的硫材料中加入少量的银/硫化银对扩散和离子传输几乎没有或没有不利影响。
此外,由于硫化银是高度稳定的化合物,因此其在阴极材料中的存在可以避免至少一些原本为锂-硫二次电池的特性的穿梭效应。
本公开不限于本文所述的示例。其中,本公开不必限于二次电池领域,而是还可以涉及其他类型的电池。换言之,除非在权利要求中陈述了特征,否则本公开还涉及本文所述的电池和装置之外的电池和其他装置。
此外,可存在其他应用,包括涉及其他活性阴极材料的应用,其中银可用于改善二次电池的性能。一种这样的应用涉及磷酸铁锂(LiFePO4或LFP)电池,其是一种锂离子电池,其中阴极包括磷酸铁锂,阳极包括石墨碳和金属背衬。与硫一样,磷酸铁锂的缺点是其低电导率。通过将磷酸铁锂结合到碳基质中可以改善阴极电导率。
然而,将碳结合到磷酸铁锂阴极中增加了阴极的厚度。随着阴极厚度的增加,离子的扩散和传输成为限制因素。因此,根据本公开,代替碳,磷酸铁锂阴极可包含少量银以显著降低阴极的质量(尺寸)同时保持其电导率。根据本公开的该方面,在其他方面类似于图1至图3中所示的电池10的电池的阴极包括以下物质的基质:(A)少量银,(B)较大量磷酸铁锂和(C)任选的一种或多种其他材料,包括例如添加剂和杂质。
Claims (16)
1.一种二次电池阴极,其中所述阴极包括掺杂材料,并且其中所述掺杂材料包含:
第一量的活性阴极材料;以及
第二量的银,其中所述第一量大于所述第二量。
2.如权利要求1所述的阴极,其中所述活性阴极材料包括硫。
3.如权利要求2所述的阴极,其中所述银为金属银或硫化银的形式。
4.如权利要求1所述的阴极,其中所述活性阴极材料包括元素硫,其中所述掺杂材料包括导电纳米颗粒的基质,并且其中所述纳米颗粒包括金属银或硫化银。
5.如权利要求1所述的阴极,其中所述活性阴极材料包括除硫之外的材料。
6.如权利要求5所述的阴极,其中所述除硫之外的材料包括磷酸铁锂。
7.一种电池,包括:
阴极;
阳极;
位于所述阴极与所述阳极之间的电解质;以及
位于所述电解质内的隔膜,用于允许离子穿过所述电解质传输到所述阴极和所述阳极以及从所述阴极和所述阳极传输;并且
其中所述阴极包括活性阴极材料和银。
8.如权利要求7所述的电池,其中所述活性阴极材料包括硫。
9.如权利要求8所述的电池,其中所述银为硫化银的形式。
10.如权利要求7所述的电池,其中所述活性阴极材料包括元素硫,其中所述活性阴极材料包括导电纳米颗粒的基质,并且其中所述纳米颗粒包括银和/或硫化银。
11.如权利要求7所述的电池,其中所述活性阴极材料包括除硫之外的材料。
12.如权利要求11所述的电池,其中所述除硫之外的材料包括磷酸铁锂。
13.一种制造阴极的方法,所述方法包括:
通过混合元素硫和银胶体产生混合物;以及
随后,从所述混合物中获得银掺杂的硫材料,其中所述银掺杂的硫材料包括银和/或硫化银。
14.如权利要求13所述的方法,进一步包括通过混合胶体银溶液与还原剂来产生所述银胶体。
15.如权利要求13所述的方法,其中所述银掺杂的硫材料包括导电纳米颗粒,并且其中所述纳米颗粒包括所述银和/或硫化银。
16.一种制造二次电池的方法,所述方法包括:提供阴极、阳极、位于所述阴极与所述阳极之间的电解质,和位于所述电解质内的隔膜;以及根据权利要求13所述的方法制造所述阴极。
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