CN112981473B - 一种电解铜箔及其制备方法 - Google Patents
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000011889 copper foil Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000460 chlorine Substances 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000011888 foil Substances 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 229920002873 Polyethylenimine Polymers 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 11
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 11
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 11
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229920002907 Guar gum Polymers 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- 239000000665 guar gum Substances 0.000 claims description 10
- 229960002154 guar gum Drugs 0.000 claims description 10
- 235000010417 guar gum Nutrition 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 235000002639 sodium chloride Nutrition 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 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
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 239000006259 organic additive Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- -1 lanthanum ions Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- LVSITDBROURTQX-UHFFFAOYSA-H samarium(3+);trisulfate Chemical compound [Sm+3].[Sm+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LVSITDBROURTQX-UHFFFAOYSA-H 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/02—Heating or cooling
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/08—Rinsing
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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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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Abstract
本发明公开了一种电解铜箔及其制备方法,属于锂离子电池铜箔技术领域,所述电解铜箔中铜含量≥99.9wt%,氯元素含量为210~260μg/g,稀土元素含量为300~340μg/g;所述制备方法包括:向硫酸‑硫酸铜溶液中加入添加剂,作为电解液进行电解,将得到的生箔经洗涤、干燥得到所述电解铜箔;本发明的电解铜箔中氯元素的含量较高,使得电解液中的有机添加剂能够更好地吸附于基材上,并通过对电解铜箔制备时电解液成分及含量进行调整,从而使所得铜箔具有良好的拉伸性能及耐折叠性。
Description
技术领域
本发明属于锂离子电池铜箔技术领域,具体涉及一种电解铜箔及其制备方法。
背景技术
锂离子二次电池具备高能量及高功率密度,使其作为便携式电子装置、电动工具、电动汽车、能量储存***、移动电话、平板电脑、航空航天应用、军事应用及铁路的技术选择,作为锂离子电池负极材料使用的电解铜箔也因此迎来了新的发展机遇。铜箔在锂电池中既充当负极活性物质的载体,又充当负极电子流的收集与传输体,因此电解铜箔的抗拉强度、延伸性、致密性、耐折叠性、表面粗糙度、厚度均匀性及外观质量等对锂离子电池负极制作工艺和锂离子电池的电化学性能有着很大的影响。
单纯的铜箔不能满足高性能要求,通常需要在电解液中加入添加剂以赋予铜箔相应的性能,而在使有机添加剂时,为使其有效吸附于铜箔需要Cl,这是因为Cl-会吸附在铜基材表面,而Cu+-有机添加剂的络合物会静电吸附于Cl-,即,Cu+-有机添加剂的络合物经由Cl-吸附于铜基材上。而且Cl的添加有利于铜箔拉伸性能的提升,但是当Cl含量超过200μg/g时,却会导致铜箔耐折叠性能的急剧下降,因此,如何在提高铜箔中Cl含量,使其能够充分发挥对有机添加剂的吸附作用及对铜箔拉伸性能的提升作用的同时,不影响铜箔的耐折叠性,是亟待解决的技术问题。
发明内容
为解决现有技术中的上述问题,本发明提供了一种电解铜箔及其制备方法。
为实现上述目的,本发明提供了如下技术方案:
本发明的技术方案之一:一种电解铜箔,铜含量≥99.9wt%,氯元素含量为210~260μg/g,稀土元素含量为300~340μg/g。
进一步地,铜含量≥99.9wt%,氯元素含量为220~240μg/g,稀土元素含量为310~320μg/g。
本发明的技术方案之二:一种上述电解铜箔的制备方法,包括以下步骤:向硫酸-硫酸铜溶液中加入添加剂,作为电解液进行电解,将得到的生箔经洗涤、干燥得到所述电解铜箔;所述添加剂包括氧化石墨烯、瓜尔胶、稀土元素的可溶性盐、羟丙基甲基纤维素、聚乙二醇、聚乙烯亚胺及含氯化合物。
进一步地,所述稀土元素为镧、铈、钐、钇中的一种;所述含氯化合物为氯化钠、氯化钾、氯化铵、氯化氢、氯化镁、氯化钙中的一种或几种。
进一步地,所述聚乙二醇的分子量为4000~6000;所述聚乙烯亚胺的分子量为6000~8000。
进一步地,所述电解液中,Cu2+的浓度为50~100g/L,硫酸的浓度为120~200g/L。
进一步地,所述电解液中,氧化石墨烯的浓度为3~6mg/L,瓜尔胶的浓度为10~15mg/L,稀土元素的浓度为40~60mg/L,羟丙基甲基纤维素的浓度为5~10mg/L,聚乙二醇的浓度为5~10mg/L,聚乙烯亚胺的浓度为30~40mg/L,Cl-的浓度为20~30mg/L。
进一步地,所述电解液温度为50~60℃,阴极电极面的平均电流密度为50~65A/dm2。
进一步地,所述洗涤为先进行水洗,再依次经过稀盐酸洗、水洗。
与现有技术相比,本发明具有以下有益效果:
(1)本发明的电解铜箔中铜含量≥99.9wt%,氯元素含量为210~260μg/g,稀土元素含量为300~340μg/g,氯元素的含量较高,使得电解液中的有机添加剂能够更好地吸附于基材上,并通过对电解铜箔制备时电解液成分及含量进行调整,从而使所得铜箔具有良好的拉伸性能及耐折叠性;
(2)本发明制备工艺简单,原料易得,生产成本低,适于推广。
具体实施方式
现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。
另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。
在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见的。本发明说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。
本发明中所述的“份”如无特别说明,均按重量份计。
实施例1
电解铜箔的制备,包括以下步骤:
配制硫酸浓度为160g/L、Cu2+的浓度为80g/L的硫酸-硫酸铜溶液,向该溶液中加入氧化石墨烯、瓜尔胶、硫酸镧、羟丙基甲基纤维素、分子量为5000的聚乙二醇、分子量为7000的聚乙烯亚胺及氯化钠作为电解液进行电解,电解液中氧化石墨烯的浓度为5mg/L、瓜尔胶的浓度为12mg/L、镧离子的浓度为50mg/L、羟丙基甲基纤维素的浓度为8mg/L、聚乙二醇的浓度为7mg/L、聚乙烯亚胺的浓度为35mg/L、氯离子的浓度为25mg/L;电解液的温度为55℃,阴极电极面的平均电流密度为60A/dm2,待阴极辊上的生箔随辊筒转出液面后,再连续地从阴极辊上剥离,经水洗后,再用稀盐酸洗,之后再次水洗后,干燥得到所述电解铜箔。对所得电解铜箔中的铜元素、氯元素及镧元素的含量进行检测,所得结果如表1所示。
实施例2
电解铜箔的制备,步骤如下:
配制硫酸浓度为120g/L、Cu2+的浓度为100g/L的硫酸-硫酸铜溶液,向该溶液中加入氧化石墨烯、瓜尔胶、硫酸铈、羟丙基甲基纤维素、分子量为4000的聚乙二醇、分子量为8000的聚乙烯亚胺及氯化铵作为电解液进行电解,电解液中氧化石墨烯的浓度为3mg/L、瓜尔胶的浓度为15mg/L、铈离子的浓度为40mg/L、羟丙基甲基纤维素的浓度为10mg/L、聚乙二醇的浓度为5mg/L、聚乙烯亚胺的浓度为30mg/L、氯离子的浓度为30mg/L;电解液的温度为50℃,阴极电极面的平均电流密度为50A/dm2,待阴极辊上的生箔随辊筒转出液面后,再连续地从阴极辊上剥离,经水洗后,再用稀盐酸洗,之后再次水洗后,干燥得到所述电解铜箔。对所得电解铜箔中的铜元素、氯元素及镧元素的含量进行检测,所得结果如表1所示。
实施例3
电解铜箔的制备,包括以下步骤:
配制硫酸浓度为200g/L、Cu2+的浓度为50g/L的硫酸-硫酸铜溶液,向该溶液中加入氧化石墨烯、瓜尔胶、硫酸钐、羟丙基甲基纤维素、分子量为6000的聚乙二醇、分子量为6000的聚乙烯亚胺及氯化镁作为电解液进行电解,电解液中氧化石墨烯的浓度为6mg/L、瓜尔胶的浓度为10mg/L、钐离子的浓度为60mg/L、羟丙基甲基纤维素的浓度为5mg/L、聚乙二醇的浓度为10mg/L、聚乙烯亚胺的浓度为40mg/L、氯离子的浓度为20mg/L;电解液的温度为60℃,阴极电极面的平均电流密度为65A/dm2,待阴极辊上的生箔随辊筒转出液面后,再连续地从阴极辊上剥离,经水洗后,再用稀盐酸洗,之后再次水洗后,干燥得到所述电解铜箔。对所得电解铜箔中的铜元素、氯元素及镧元素的含量进行检测,所得结果如表1所示。
对比例1
同实施例1,区别在于,电解液中不加入羟丙基甲基纤维素。
对比例2
同实施例1,区别在于,电解液中镧离子的浓度为80mg/L。
对比例3
同实施例1,区别在于,电解液中氯离子含量为10mg/L。
对比例4
同实施例1,区别在于,所采用的聚乙二醇的分子量为8000。
对比例5
同实施例1,区别在于,所采用的聚乙烯亚胺的分子量为10000。
表1
组别 | 含铜量/wt% | Cl含量/(μg/g) | 稀土元素含量/(μg/g) |
实施例1 | 99.93 | 225.3 | 314.8 |
实施例2 | 99.96 | 251.7 | 305.2 |
实施例3 | 99.91 | 214.6 | 331.4 |
对比例1 | 99.92 | 223.5 | 310.5 |
对比例2 | 99.89 | 221.5 | 332.8 |
对比例3 | 99.97 | 198.5 | 318.2 |
对比例4 | 99.92 | 226.1 | 312.5 |
对比例5 | 99.93 | 220.5 | 319.7 |
效果验证
1)拉伸性能
使用拉伸试验机分别对实施例1~3及对比例1~6制备的电解铜箔的拉伸性能及惰性气体氛围下,350℃加热1h后的拉伸性能进行测定,所得抗拉强度如表2所示。
2)耐折叠性
在室温下,对实施例1~3及对比例1~6制备的电解铜箔及对其在惰性气体氛围下,350℃加热1h后进行折叠试验,首先使用厚度100μm的聚酰亚胺薄膜作为弯曲半径为0.2mm的隔层,将各组样品置于该隔层上,得到样品与隔层的折叠体;然后,对该折叠体进行弯折,使得隔层位于内侧,样品位于外侧,即:弯折后共形成4层,内部两层为所述聚酰亚胺薄膜隔层,上下外层均为样品;之后使用橡胶制辊(重量2kg,橡胶硬度80Hs)对其上层施加载荷,使用光学显微镜观察样品是否出现裂缝;若无裂缝,则再次打开,重复上述步骤,直至观察到裂缝产生,记录折叠次数,如表2所示。
表2
由表1及表2可以看出,本发明的电解铜箔中Cl含量高于200μg/g,且铜箔同时具有优良的拉伸性能及耐折叠性。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明披露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围内。
Claims (5)
1.一种电解铜箔,其特征在于,铜含量≥99.9wt%,氯元素含量为210~260μg/g,稀土元素含量为300~340μg/g;
所述电解铜箔的制备方法,包括以下步骤:向硫酸-硫酸铜溶液中加入添加剂,作为电解液进行电解,将得到的生箔经洗涤、干燥得到所述电解铜箔;所述添加剂包括氧化石墨烯、瓜尔胶、稀土元素的可溶性盐、羟丙基甲基纤维素、聚乙二醇、聚乙烯亚胺及含氯化合物;
所述聚乙二醇的分子量为4000~6000;所述聚乙烯亚胺的分子量为6000~8000;
所述电解液中,Cu2+的浓度为50~100g/L,硫酸的浓度为120~200g/L;
所述电解液中,氧化石墨烯的浓度为3~6mg/L,瓜尔胶的浓度为10~15mg/L,稀土元素的浓度为40~60mg/L,羟丙基甲基纤维素的浓度为5~10mg/L,聚乙二醇的浓度为5~10mg/L,聚乙烯亚胺的浓度为30~40mg/L,Cl-的浓度为20~30mg/L。
2.根据权利要求1所述的电解铜箔,其特征在于,铜含量≥99.9wt%,氯元素含量为220~240μg/g,稀土元素含量为310~320μg/g。
3.根据权利要求1所述的电解铜箔,其特征在于,所述稀土元素为镧、铈、钐、钇中的一种;所述含氯化合物为氯化钠、氯化钾、氯化铵、氯化氢、氯化镁、氯化钙中的一种或几种。
4.根据权利要求1所述的电解铜箔,其特征在于,所述电解液温度为50~60℃,阴极电极面的平均电流密度为50~65A/dm2。
5.根据权利要求1所述的电解铜箔,其特征在于,所述洗涤为先进行水洗,再依次经过稀盐酸洗、水洗。
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