CN1529919A - 电池 - Google Patents
电池 Download PDFInfo
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- CN1529919A CN1529919A CNA028089464A CN02808946A CN1529919A CN 1529919 A CN1529919 A CN 1529919A CN A028089464 A CNA028089464 A CN A028089464A CN 02808946 A CN02808946 A CN 02808946A CN 1529919 A CN1529919 A CN 1529919A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 82
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000008187 granular material Substances 0.000 claims description 76
- 239000003054 catalyst Substances 0.000 claims description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- 239000011701 zinc Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims 3
- 150000001721 carbon Chemical class 0.000 claims 2
- 239000003570 air Substances 0.000 claims 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 claims 1
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- 239000007800 oxidant agent Substances 0.000 abstract description 6
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
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- 239000011572 manganese Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
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- 239000002184 metal Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
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- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
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- 239000004698 Polyethylene Substances 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229960004424 carbon dioxide Drugs 0.000 description 2
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- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
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- 238000009279 wet oxidation reaction Methods 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 239000011398 Portland cement Substances 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
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- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- 239000003273 ketjen black Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
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Images
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/023—Gel electrode
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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Abstract
一种制造具有阴极的电池的方法,该方法包括使碳颗粒与氧化剂如无机酸、有机酸或氧化气体接触;和将该碳颗粒掺入到阴极内。所述阴极可例如在包括单层或双层阴极的金属-空气电池内或在燃料电池内使用。
Description
本发明涉及电池。
电池通常用作电能源。电池含有负极,典型地称为阳极,和正极,典型地称为阴极。阳极含有可被氧化的活性材料;阴极含有或消耗可被还原的材料。阳极活性材料能还原阴极活性材料。为了防止阳极材料与阴极材料直接反应,阳极和阴极彼此通过分隔器进行电分离。
若电池用作器件如蜂窝式电话内的电能源,则使阳极和阴极进行电接触,从而使电子流过器件和允许各自的氧化和还原反应发生,以提供电源。与阳极和阴极接触的电解质含有离子,离子通过分隔器在电极之间流动,以维持放电过程中整个电池中的电荷平衡。
在金属-空气电化学电池中,通过电池容器内的一个或多个空气入口,从电池外的大气向阴极供应氧气。氧气是活性材料,它在阴极处被还原成氢氧根离子,阴极可包括承载在碳颗粒上的催化剂。金属例如锌是另一种活性材料,它在阳极处被氧化。
当在器件例如高功率器件内使用时,希望电化学电池能承载良好的电流密度。
本发明涉及电池,如金属-空气电池,例如当在高速率应用中使用时,它可维持相对高的电流密度,同时具有相对最小的电压降。
一方面,本发明的特征在于阴极,它包括碳颗粒例如炭黑,其中例如通过使碳颗粒与氧化剂如无机酸或有机酸接触而使之暴露于氧化条件下。由于碳颗粒被氧化,所以它们具有酸性的表面官能团、氧化的碳官能度和/或低pH,例如小于约7或介于约2至约4。
不希望受到理论的束缚,认为氧化的碳颗粒具有化学改性的表面,它的极性比未氧化的碳颗粒大。氧化的碳颗粒比未氧化的碳颗粒能将更多的电解质吸入到阴极内,这是因为电解质可更容易地湿式氧化具有极性表面的颗粒,而电解质可能不那么容易地湿式氧化具有极性相对较小的表面的颗粒。结果更多的阴极可有效地用于电池内发生的还原-氧化反应。
当将氧化的碳颗粒掺入到电池如金属-空气电池的阴极内时,它们通常提供电池相对高的速率,这对高功率器件来说是有用的。阴极具有良好的物理完整性,具有最小的裂纹和/或孔洞。在阴极具有双层结构的实施方案中,阴极具有相对低的阻抗、良好的粘结和良好的内聚力。双层阴极在提供良好的电流性能的同时,也可提供良好的防护,防止电解质渗透和泄漏,例如当阴极具有带氧化的碳颗粒的层和带有未氧化的碳颗粒的层时。带有氧化的碳颗粒的阴极通常相对简单和便于制造。
另一方面,本发明的特征在于制造具有阴极的电池的方法,该方法包括使碳颗粒与无机酸或有机酸接触,和将碳颗粒掺入到阴极内。阴极可进一步包括二氧化锰和聚四氟乙烯。阴极可以是单层阴极或双层阴极。电池可以是金属-空气电池如锌-空气电池。
另一方面,本发明的特征在于用于金属-空气电池的阴极。阴极可包括第一层和第二层,其中第一层具有未用酸处理的碳颗粒,和第二层具有已经用酸处理的碳颗粒。各层可包括催化剂和/或聚合物,如聚四氟乙烯。
此处所使用的“氧化的碳颗粒”是指暴露于氧化条件,例如与氧化剂接触的碳颗粒。例如,氧化的碳颗粒可具有增加的酸性表面氧化物或官能团、氧化的碳官能度和/或低pH。“未氧化的碳颗粒”是指不具有暴露于氧化条件下的碳颗粒。
根据说明书、附图和根据权利要求,本发明的其它特征、目的和优点将变得显而易见。
附图是金属-空气电池的立剖面视图。
参考附图,圆柱形金属-空气电池10包括具有空气入口14的外壳12、阴极管16、阳极18和在阴极管16与阳极18之间的分隔器20。电池10进一步包括阳极集电器22、封装组件24和金属顶帽26。
阴极管16包括一种或多种催化剂的共混物、碳颗粒和粘合剂。
由可催化氧气还原和/或催化过氧化物分解的细分的金属颗粒和/或金属氧化物制造催化剂。这些催化剂包括,但不限于锰化合物、贵金属、金属杂环、钴及其混合物。催化剂优选包括锰氧化物如Mn2O3、Mn3O4和MnO2,因为它们可消除阴极内的过氧化物,从而减少电压的下降。可例如通过加热硝酸锰或还原高锰酸钾制备含锰氧化物的催化剂。也可使用可商购的锰氧化物,如以Faridiser M形式获自Sedema的化学合成的二氧化锰(CMD)。催化剂优选具有相对小的粒度(例如通过研碎催化剂颗粒成约1-2微米的平均粒度)、相对高的表面积(例如大于100m2/g)和相对高的孔隙率。催化剂颗粒可分散在载体如碳上。催化剂的负载可从0.1wt%变化到20wt%。
碳颗粒包括用一种或多种强氧化剂处理过的碳颗粒。认为氧化剂提高在碳颗粒上酸性表面氧化物如碳-氧表面结构的浓度。氧化的碳颗粒可具有例如氧化的碳官能度和/或酸性的表面官能团如羧酸、内酯酸和酚酸。包括酸性表面氧化物的一些碳颗粒可商购得到,例如Monarch 1300,据报道它的pH为约2-4(获自Cabot Corp.(Billerica,MA)),和Degussa FW-18(获自Degussa Düls AG(德国))。
另外,可通过将未氧化的碳颗粒暴露于氧化条件,例如与氧化剂接触,形成氧化的碳颗粒。非增强的碳颗粒的实例包括Black Pearls2000,Vulcan XC-72(Cabot Corp.,Billerica,MA)、ShawiniganAcetylene Black(Chevron,San Francisco,CA)和Ketjen Black(Akzo Nobel,Chicago,IL)。据报道,这些未氧化的碳颗粒中的一些具有介于约6至约8的pH。例如通过用无机酸和/或有机酸处理碳颗粒,可在碳颗粒上形成酸性表面官能团和/或氧化的碳官能度,从而可提供这些未氧化的碳颗粒增加的酸性表面氧化物。无机酸可以包括例如硝酸、硫酸、盐酸、磷酸及其混合物。有机酸可包括例如过乙酸、三氟乙酸及其混合物。其它化学氧化剂包括例如KMnO4和KClO3。
根据下述例举步骤制备氧化的碳颗粒的样品。75g未氧化的碳颗粒(Vulcan XC-72)与1L水和500ml硝酸(试剂级,70%)的溶液混合。在搅拌下,在约60℃下加热混合物约1小时。在冷却到室温之后,使用两层耐酸滤纸过滤混合物。将分离的碳颗粒转移到大烧杯中,使之与1.5L去离子水混合至少30分钟并过滤。用去离子水洗涤碳颗粒,有时达到9-10次,直到滤液的pH为约5-6。然后,在80℃下,在A类(Class A)烘箱中干燥碳颗粒过夜。然后用研钵和杵子研磨碳颗粒的干燥滤饼。
粘合剂的实例包括聚乙烯粉末、聚丙烯酰胺、卜特兰水泥和氟碳树脂,如聚偏氟乙烯和聚四氟乙烯。聚乙烯粘合剂的实例是以商标Coathylene HA-1681(获自Hoechst)销售的。优选的粘合剂包括聚四氟乙烯(PTFE)颗粒。粘合剂可使阴极相对耐湿,从而降低电解质从电池中泄漏的可能性。
可使用催化剂,优选氧化的碳颗粒和粘合剂的共混物形成单层阴极和双层阴极。
在单层阴极的一些实施方案中,通过将催化剂与氧化的碳颗粒混合,然后在双行星式混合机内将该混合物与粘合剂分散液(约60重量%的固体)和异丙醇混合,形成捏塑体(约7-15重量%的固体),从而形成阴极。使用Rondo糕饼(pastry)混合机,在筛网(screen)基质如镍或镀镍的钢基质上辊压所制备的捏塑体,形成具有所需厚度的平片阴极。空气干燥辊压过的阴极,然后在300℃下,在烘箱中,在空气或真空下干燥,例如从阴极中除去任何残留的挥发物。所得阴极包括约1%-约25%的催化剂如二氧化锰(获自Sedema的Faradiser M);约25%-约94%的氧化的碳颗粒;和约5%-约50%的粘合剂(获自DuPont的PTFE,T-30)。阴极优选包括约15%-约20%的催化剂;约45%-约60%的氧化碳;和约25%-约35%的粘合剂。
对于双层阴极来说,阴极具有面对阳极凝胶18的一侧和面对空气入口14的一侧。面对阳极凝胶18的一侧有时称为活性层或催化剂层,面对空气入口14的一侧有时称为疏水层或空气层。阴极还包括集电器如金属网,它将阴极电接触到外壳上。
空气层混合物包括与聚合物如PTFE混合的任何以上列举的碳颗粒,优选未氧化的碳颗粒如Vulcan XC-72、分散液(60重量%的固体)和异丙醇。在一些实施方案中,在空气层内的未氧化的碳颗粒可使催化剂层内的电解质最小地迁移到空气层内并泄漏出电池。空气层混合物包括约50%-约80%的未氧化的碳颗粒和约20%-约50%的聚合物。空气层优选包括约60%-70%的未氧化的碳颗粒和约30%-40%的聚合物。
空气层混合物被加工成捏塑体(约30-50重量%的固体),然后使用Rondo糕饼混合机,在集电器如镍或镀镍的不锈钢筛网上辊压,形成具有所需厚度的结构体。在一些实施方案中,集电器位于空气层内或位于催化剂与空气层之间的界面处。空气干燥辊压的结构体,然后在300℃下,在烘箱中,在空气或真空下干燥,例如除去阴极中任何残留的挥发物。
通过混合催化剂与氧化的碳颗粒,然后将该混合物与粘合剂分散液(约60重量%的固体)和异丙醇在双行星式混合机内混合,形成捏塑体(约7-15重量%的固体),从而形成催化剂层混合物。所得催化剂层混合物包括约1%-约25%的催化剂如二氧化锰(获自Sedema的Faradiser M);约45%-约98%的氧化的碳颗粒;和约1%-约30%的粘合剂(获自DuPont的PTFE,T-30)。催化剂层混合物优选包括约15%-约25%的催化剂;约60%-约84%氧化的碳;和约1%-约10%的粘合剂。
然后使用Rondo糕饼混合机,在空气层/集电器结构体上辊压所制备的催化剂层混合物的捏塑体,形成具有所需厚度的双层阴极。空气干燥辊压的阴极,然后在300℃下,在烘箱中,在空气或真空下干燥,例如除去阴极中任何残留的挥发物。
然后将所形成的单层或双层阴极加工成管状。所形成的阴极如管16的外部面对电池开口14,它可被阻挡膜28如PTFE膜覆盖。膜28辅助维持电池10内的恒定湿度水平。膜28也辅助防止电解质泄漏出电池和二氧化碳进入电池内,同时维持空气的渗透率,结果氧气可扩散入电池和阴极内。在一些实施方案中,电池10还包括在膜28与空气入口14之间的空气分配器(未示出)或沾吸(blotter)材料。空气分配器是多孔或纤维材料,它辅助保持在膜28与外壳12之间的空气扩散空间。
分隔器20放置在阴极管16内。分隔器20可以是通过化学表面活性剂变得疏水的多孔电绝缘聚合物如聚丙烯,它允许电解质与阴极接触。
为了组装电池10,将阴极管16放置在容器12内,其中阴极管16被阻挡膜28和任选地空气分配器包裹,且包括分隔器20。为了封装阴极,容器12可包括导电的热熔体(未示出),如装载有碳、石墨或镍的聚酰胺。阴极集电器应当与容器12的底部电接触。可通过在阴极集电器与容器底部之间提供直接的物理接触,例如通过将集电器焊接到容器底部,从而使得电接触。或者,将导电薄片连接到集电器和容器底部二者上。阴极管16和容器12一起确定在其间的进气空间30。
在插入阴极管16之后,用阳极凝胶18填充由分隔器20和阴极管16形成的内腔。
阳极凝胶18含有锌与电解质的混合物。锌与电解质的混合物可包括胶凝剂,它辅助防止电解质从电池中泄漏并辅助锌粒在阳极内悬浮。
锌材料可以是与铅、铟、铝或铋形成合金的锌粉。例如,锌可与约400至600ppm(例如500ppm)的铅、400至600ppm(例如500ppm)的铟、或约50至90ppm(例如70ppm)的铝形成合金。优选锌材料可包括铅、铟和铝、铅和铟、或铅和铋。或者锌可包括铅,而不含另一金属添加剂。锌材料可以是空气吹制的锌或旋制(spun)的锌。例如在1998年9月18日申请的U.S.S.N09/156915、1997年8月1日申请的U.S.S.N08/905254和1998年7月15日申请的U.S.S.N09/115867中公开了合适的锌粒,在此引入每篇文献的全部内容作为参考。
锌粒可以是球形或非球形的。例如,锌粒可以是针形(长宽比至少为2)。锌材料包括大部分尺寸介于60目至325目的颗粒。例如,锌材料可具有下述粒度分布:
0-3wt%在60目筛网上;
40-60wt%在100目筛网上;
30-50wt%在200目筛网上;
0-3wt%在325目筛网上;和
0-0.5wt%在盘(pan)上。
合适的锌材料包括获自Union Miniere(Overpelt,比利时)、Duracell(美国)、Noranda(美国)、Grillo(德国)或Toho Zinc(日本)的锌。
胶凝剂是吸收剂聚丙烯酸酯。吸收剂聚丙烯酸酯具有小于约30g盐水/g胶凝剂的吸收范围(envelope),这是根据美国专利No.4541871中所述测量的,在此引入其作为参考。在阳极混合物中,阳极凝胶包括小于锌干重的1%的胶凝剂。胶凝剂的含量优选介于约0.2至约0.8重量%,更优选介于约0.3至约0.6重量%,和最优选约0.33重量%。吸收剂聚丙烯酸酯可以是通过悬浮聚合制造的聚丙烯酸钠。合适的聚丙烯酸钠的平均粒度介于约105至180微米,和pH为约7.5。例如在美国专利No.4541871、美国专利No.4590227或美国专利No.4507438中公开了合适的胶凝剂。
在一些实施方案中,阳极凝胶可包括非离子表面活性剂。表面活性剂可以是涂布在锌表面上的非离子的磷酸酯表面活性剂如非离子的磷酸烷基酯或非离子的磷酸芳基酯(如获自Rohm & Haas的RA600或RM510)。阳极凝胶可包括涂布在锌材料表面上的介于约20至约100ppm的表面活性剂。表面活性剂可充当放气抑制剂。
电解质溶液可以是氢氧化钾的水溶液。电解质可包括介于约30至约40%,优选介于35至40%的氢氧化钾。电解质也可包括介于约1至2%的氧化锌。
在阳极凝胶18放入容器12内之后,将预组装的顶部组件32放置在容器12顶部。顶部组件32包括封装件24、集电器22和焊接到集电器22上的顶帽26。由合适的金属如黄铜制造集电器22。可例如由尼龙制造封装件24。将额外的非导电的热熔体(BiWax Corp.)放置在封装件24与阴极管16之间,以使电解质和阳极材料的泄漏最小。然后在预组装的顶部组件32上向下锻模容器12的上部外周(即唇边),以便在容器12的顶部封装顶部组件32。
在储存过程中,可用覆盖电池开口14的可回收片材覆盖电池10。片材,例如不透氧和透氢片材限制电池内外之间的空气流动。用户在使用之前从电池上剥掉片材,以允许空气中的氧气进入电池内部。也可在密封的金属袋中储存电池。用户在使用之前从袋中取出电池。
在1999年8月13日申请的U.S.S.N09/374277、1999年8月13日申请的U.S.S.N09/374278、1999年10月13日申请的U.S.S.N09/416799、1999年10月26日申请的U.S.S.N09/427371和2000年1月31日申请的U.S.S.N09/494586中公开了金属-空气电池的其它实施方案及其制造方法,在此引入所有这些文献的全部内容作为参考。
在其它实施方案中,可通过使用其它化学方法提高阴极的润湿性。例如,阴极可包括表面活性剂,阴极可包括极性添加剂,以使未氧化的碳颗粒更加可润湿;和阴极可包括亲水聚合物如聚乙烯醇。可通过使碳颗粒与氧化气体例如以上列举的酸的气体形式、空气(例如介于350-700℃)、NO2/空气、NO/氧气、氧气、N2O、CO2和臭氧接触,使未氧化的碳颗粒被氧化。其它碳颗粒可包括例如活性炭如Calgon PWA(Calgon Carbon,Pittsburgh,PA)。双层阴极的空气层可包括氧化的碳颗粒。电池10可包括菱形电池、钮扣电池和其它形式的金属-空气电池。
在一些实施方案中,可将如上所述的氧化的碳颗粒掺入到燃料电池内的一个或多个空气电极中。
其它实施方案见权利要求。
Claims (25)
1.一种制造具有阴极的电池的方法,该方法包括:
使碳颗粒与无机酸接触;和
将该碳颗粒掺入到阴极内。
2.权利要求1的方法,其中碳颗粒在与无机酸接触之后,其pH小于约7。
3.权利要求1的方法,其中碳颗粒在与无机酸接触之后,其pH介于约2至约4。
4.权利要求1的方法,进一步包括将二氧化锰掺入到阴极内。
5.权利要求4的方法,进一步包括将聚四氟乙烯掺入到阴极内。
6.权利要求5的方法,其中阴极包括:
约25%-约94重量%的碳颗粒;
约1%-约25重量%的催化剂;和
约5%-约50重量%的聚合物。
7.权利要求5的方法,其中阴极包括:
约45%-约60重量%的碳颗粒;
约15%-约20重量%的催化剂;和
约25%-约35重量%的聚合物。
8.权利要求1的方法,其中无机酸包括硫酸。
9.权利要求1的方法,其中无机酸包括硝酸。
10.权利要求1的方法,其中阴极是双层阴极。
11.权利要求10的方法,进一步包括将未与酸接触的碳颗粒掺入到双层阴极内。
12.权利要求1的方法,其中电池是金属-空气电池。
13.权利要求1的方法,其中电池包括含锌的阳极。
14.一种制造具有阴极的电池的方法,该方法包括:
使碳颗粒与氧化气体接触;和
将该碳颗粒掺入到阴极内。
15.权利要求14的方法,其中氧化气体包括选自空气、氧气、二氧化碳、氮氧化物和臭氧中的物质。
16.权利要求14的方法,其中阴极是双层阴极。
17.一种金属-空气电池用的阴极,该阴极包括:
第一层和第二层,所述第一层包括:未与酸接触的碳颗粒和第一有机聚合物;和所述第二层包括:已经与酸接触的碳颗粒和第二有机聚合物;
其中第一层和第二层彼此接触。
18.权利要求17的阴极,其中已经与酸接触的碳颗粒的pH小于约7。
19.权利要求17的阴极,其中已经与酸接触的碳颗粒的pH介于约2至约4。
20.权利要求17的阴极,其中第二层进一步包括催化剂。
21.权利要求20的阴极,其中催化剂包括二氧化锰。
22.权利要求17的阴极,其中:
第一层包括:约50%-约80重量%的未与酸接触的碳颗粒;和约20%-约50重量%的第一有机聚合物;和
第二层包括:约45%-约98重量%的已经与酸接触的碳颗粒;和约1%-约30重量%的第二有机聚合物。
23.权利要求17的阴极,其中:
第一层包括:约60%-约70重量%的未与酸接触的碳颗粒;和约30%-约40重量%的第一有机聚合物;和
第二层包括:约60%-约84重量%的已经与酸接触的碳颗粒;和约1%-约10重量%的第二有机聚合物。
24.权利要求21的阴极,其中第二层进一步包括约1%-约25重量%的催化剂。
25.权利要求21的阴极,其中第一和第二有机聚合物包括聚四氟乙烯。
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US09/843,641 US6593023B2 (en) | 2001-04-27 | 2001-04-27 | Battery and method of making the same |
US09/843,641 | 2001-04-27 |
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US (1) | US6593023B2 (zh) |
EP (1) | EP1390997A2 (zh) |
JP (1) | JP2005510829A (zh) |
CN (1) | CN100367550C (zh) |
AU (1) | AU2002307333A1 (zh) |
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-
2001
- 2001-04-27 US US09/843,641 patent/US6593023B2/en not_active Expired - Lifetime
-
2002
- 2002-04-16 JP JP2002586429A patent/JP2005510829A/ja active Pending
- 2002-04-16 WO PCT/US2002/011916 patent/WO2002089239A2/en active Application Filing
- 2002-04-16 CN CNB028089464A patent/CN100367550C/zh not_active Expired - Fee Related
- 2002-04-16 BR BR0209078-3A patent/BR0209078A/pt not_active Application Discontinuation
- 2002-04-16 EP EP02766769A patent/EP1390997A2/en not_active Withdrawn
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CN100367550C (zh) | 2008-02-06 |
JP2005510829A (ja) | 2005-04-21 |
WO2002089239A2 (en) | 2002-11-07 |
BR0209078A (pt) | 2006-02-07 |
US6593023B2 (en) | 2003-07-15 |
US20020160251A1 (en) | 2002-10-31 |
EP1390997A2 (en) | 2004-02-25 |
WO2002089239A3 (en) | 2003-12-04 |
AU2002307333A1 (en) | 2002-11-11 |
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