CN1052578C - 拉浆式金属氢化物电极的制备方法 - Google Patents
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- 229910052987 metal hydride Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000004681 metal hydrides Chemical class 0.000 title abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011232 storage material Substances 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 15
- 239000011149 active material Substances 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 239000004020 conductor Substances 0.000 claims description 3
- 238000007790 scraping Methods 0.000 claims description 3
- 229920003091 Methocel™ Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 238000010924 continuous production Methods 0.000 abstract description 2
- 238000005096 rolling process Methods 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 1
- 239000006258 conductive agent Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
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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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/26—Processes of manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
本发明公开一种拉浆式金属氢化物电极的制备方法,以穿孔金属带为骨架,MC和聚乙烯醇缩甲醛为粘合剂,石墨粉、镍粉为导电剂,混合稀土贮氢材料为活性物质,再按比例将其和浆,并均匀地涂在金属带两侧,经干燥、辊压完成极板成型。利用本发明能实现连续生产极板带,再经模具落料制成电极片。该电极柔软、韧性高,宜卷绕成型,与烧结镍电极相匹配,制成的AA型MH/Ni电池,平均容量可达1150mAh,循环寿命按IEC方法可达950次。
Description
本发明涉及一种电极的制备方法,特别涉及一种拉浆式金属氢化物电极的制备方法。
1990年日本松下等公司相继建成MH/Ni电池试生产线,在US4,935,318、US5,034,289、US4,898,794中公开了一种利用泡沫镍或镍纤维毡为骨架,以聚乙烯醇为粘合剂的涂膏方法,填充物质后加压成型极板,制成金属氢化物电极。不足之处是加压成型极板强度受到限制,利用泡沫导致手工操作多,未能实现连续化生产,存在生产效率低;极组卷绕时废品率>5%,价格高等缺点。在US5,008,164公开特许电极(A)平3-93160中公开一种以穿孔金属带为骨架,以聚四氟乙烯乳液或聚四氟乙烯粉PTFE为粘合剂,将PTFE作成乳液与贮氢合金粉、添加剂等均匀混合在一起制成浆状粘稠体后成型,经干燥、加压制成金属氢化物电极。不足之处是电极内阻较大。
本发明的目的是提供一种用穿孔金属带为骨架,以甲基纤维素和聚乙烯醇缩甲醛溶液为粘合剂,混合稀土贮氢材料为活性物质,镍粉和石墨粉为导电材料制备金属氢化物电极的方法,能实现电极的均匀性、高合格率和大规模连续化生产。
本发明的目的可以通过以下措施来达到:以穿孔金属带为骨架,采用混合稀土贮氢材料为活性物质,镍粉、石墨粉为导电材料,其重量百分比为80~90∶9~17∶1~3制成负极活性物质;甲基纤维素和聚乙烯醇缩甲醛溶液的重量百分比为1∶1制成粘合剂。然后将负极活性物质与粘合剂按重量百分比100∶33~40和浆,通过刮浆工装将活性物质浆液均匀地涂在金属带两侧,经干燥、辊压、模具落料制成金属氢化物电极片。
该电极的成型工艺过程中:
负极活性物质的制备:将混合稀土贮氢合金材料、镍粉、石墨粉的重量百分比为80~90∶9~17∶1~3混合均匀。
粘合剂的制备:配制浓度为2~8Wt%的甲基纤维素(MC)溶液,同时将聚乙烯醇缩甲醛溶液预先调到PH值为6~7,然后按MC溶液和聚乙烯醇缩甲醛溶液的重量百分比为1∶1混合均匀成为MC聚乙烯醇缩甲醛胶。
和浆:将备好的负极活性物质与粘合剂的重量百分比为100∶33~40混合搅拌均匀。
本发明拉浆式金属氢化物电极的制备方法,能连续拉制数百米长的金属氢化物电极带,不仅实现了连续成型生产,提高了生产效率,每小时可生产720片负极。同时由平整的穿孔金属带骨架通过有贮氢合金浆液粘度的浆槽,再经稳定温度的烘干,确保了极板的均匀性和合格率>95%。该电极柔软、韧性高,特别适宜卷绕成型,可反复卷绕3~5次不破损和断裂。
附图的图面说明如下:
图1是本发明拉浆式金属氢化物电极的制备工艺流程图。
图2是制备拉浆式金属氢化物电极板成型的设备示意图。
图3、图4是AA型MH/Ni电池的放电曲线。
下面将结合具体的实施方式及其附图对本发明作进一步详述:
图1中按负极活性物质与粘合剂的重量百分比为100∶33~40和浆,首先将配制好的粘合剂1倒入和浆设备,然后在有机械搅拌的情况下,逐渐缓慢地加入已混合均匀的负极活性物质3,经3小时以上,直至将合金浆2混合均匀。用厚度0.03~0.08mm的穿孔金属带为骨架,通过常用刮浆工装将活性物质均匀地涂在金属带两侧拉浆成型5,再通过干燥6,使极板中所含水份蒸发掉,再经辊压7完成极板成型。然后由模具落料8制成金属氢化物电极片9。
在制备金属氢化物电极板成型设备图2中,将和好的贮氢合金浆液注入浆槽10,将烘干炉15、17升温到80~140℃,然后开车,穿孔金属带骨架11从金属带复绕装置12松开后通过贮存槽10的导向轮13,骨架两侧挂满浆液后通过刮浆板14,调整刮浆板间隙实现控制极板成型浆层厚度满足需要,再通过烘干炉15、导向轮16、烘干炉17,将极板中所含水份蒸发掉,又经导轮18导向后经双辊压机19滚压完成极板成型,极带厚<0.7~1mm,由电极复绕盘20收卷。
将电极带落料后制成长度为95mm,宽40mm,厚0.35mm,活性物质重量为6.5克的金属氢化物负电极片与采用传统的湿法成型工艺制成长75mm、宽39mm,厚0.68mm,活性物质N(OH)2,重量为3.5~3.8克的烧结式镍电极相匹配,可选用维尼纶无纺布双层复合隔膜180×41×0.02(mm)3夹在正负极板之间,卷绕成极组,装壳、加电流、密封制成AA型MH/Ni电池。然后以0.2C电流进行充、放电,封口化成。C为蓄电池的额定容量。该电池平均容量可达1150mAh,循环寿命按IEC方法可达950次。其电池性能如下:
外形尺寸:(带塑料管)直径 Φ14.5-1.5
高度 50-2.0
重量≤26克
额定容量1000mAh
放电性能见表:
环境温度 | 放电电流A | 最大容量mAh | 最小容量mAh | 平均容量mAh |
室温 | 0.2C放电 | 1190 | 1110 | 1150 |
室温 | 1C | 1130 | 1030 | 1050 |
室温 | 3C | 1140 | 1080 | 1110 |
室温 | 5C | 1080 | 920 | 1060 |
-18℃ | 0.2C | 1070 | 970 | 1000 |
-18℃ | 1C | 950 | 850 | 870 |
-18℃ | 2C | 850 | 830 | 845 |
28天自放后 | 0.2C | 846 | 750 | 788 |
图3、图4均为AA型MH/Ni电池的不同倍率以0.4C5电流放电,放电3.5小时的过程中放出容量占电池额定容量的百分数多少与电池电压变化的情况。图3是电池在常温18℃~23℃下倍率为0.2C5A、1C5A、3C5A和5C5A的放电线是21、22、23和24。
图4为AA型MH/Ni电池在低温-18℃~-20℃下,倍率为0.2C5A的放电曲线是25;倍率为1C5A的放电曲线是26。
Claims (1)
1.一种金属氢化物电极的制备方法,以穿孔金属带为骨架(4),其特征是采用混合稀土贮氢材料为活性物质,镍粉、石墨粉为导电材料其重量百分比为80~90∶9~17∶1~3制成负极活性物质(3),由浓度为2~8Wt%的甲基纤维素溶液与聚乙烯醇缩甲醛溶液PH值为6~7的重量百分比为1∶1制成粘合剂(1),然后将负极活性物质(3)与粘合剂(1)按重量百分比100∶33~40和浆(2),通过刮浆工装将活性物质浆液均匀地涂在金属带两侧(5),再经干燥(6),辊压(7),模具落料(8)制成金属氢化物电极片(9)。
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CN1076313A (zh) * | 1992-03-09 | 1993-09-15 | 江门三捷电池实业有限公司 | 镍氢电池及其制造技术 |
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