CN103199261A - Modification method of negative current collector copper foil of lithium ion battery - Google Patents
Modification method of negative current collector copper foil of lithium ion battery Download PDFInfo
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- CN103199261A CN103199261A CN2013100715512A CN201310071551A CN103199261A CN 103199261 A CN103199261 A CN 103199261A CN 2013100715512 A CN2013100715512 A CN 2013100715512A CN 201310071551 A CN201310071551 A CN 201310071551A CN 103199261 A CN103199261 A CN 103199261A
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Abstract
The invention belongs to the technical field of lithium ion battery, concretely relates to a modification method of carbon-coated negative current collector copper foil of the lithium ion battery. A carbon layer coated on surface of the copper foil has a thickness of 15-28 micrometers, and a ratio of carbon-coated area is 50-85 %. The method comprises polishing the copper foil with a thickness of 20-30 micrometers by using a sand paper; wiping the surface of the polished copper foil with alcohol cotton so as to clean foreign materials on the surface and a surface oxide layer; using an electric spark discharge technology with a graphite rod as a conductive electrode A of an electric spark working machine and the copper foil as the other electrode B of the electric spark working machine, so that the graphite electrode can discharge at tips of the copper foil surface and a ratio of carbon-coated area on the copper foil surface is 50-85 % per unit area; and sweeping non-fixed carbon particles with a brush, thereby preparing the carbon-coated negative current collector copper foil of the lithium ion battery. The copper foil is carburized on the surface, thereby mainly improving conductivity of the current collector, and also improving plasticity, roughness, corrosion resistance and wear resistance of the copper foil surface.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of modification processing method of lithium ion battery negative copper foil of affluxion body.
Background technology
Early stage lithium ion battery adopts rolled copper foil as negative current collector more, but along with the development of battery production technology and the raising of electrolytic copper foil performance, and at present domestic and international most of lithium ion battery producer adopts electrolytic copper foil to make the battery cathode collector more.Cathode copper is as the negative current collector of lithium ion battery, and Copper Foil had both served as the carrier of negative electrode active material in battery, serves as the collection and transmission body of negative pole electron stream again.For negative pole, except negative active core-shell material, the characteristic of Copper Foil and quality are huge to battery performance and the influence of negative pole manufacture craft.The hydrophily of Copper Foil is relevant with itself qualification structure and rough surface, directly have influence on engagement capacity, adhesive ability, electrode manufacturing process and electrode quality with negative electrode active material, electrolytic copper foil anticathode active material must possess adhesion strength preferably, do not come off in order to apply negative electrode active material uniformly, otherwise the life-span that can have influence on the internal resistance of cell and recycle.So, require copper foil surface that certain degree of roughness is arranged.
Summary of the invention
The present invention mainly is the surface for the negative current collector Copper Foil of handling lithium ion battery, increases the conductivity of collector, reduces the internal resistance of battery, increases the useful life of battery.The modification processing method that the purpose of this invention is to provide a kind of lithium ion battery negative copper foil of affluxion body.
The present invention adopts following scheme to realize:
A kind of lithium ion battery negative copper foil of affluxion body, it is to adopt the spark discharge technology to inlay carbon nano-particle at copper foil surface, and making the thickness of the carbon-coating that copper foil surface inlays is 15～28 microns, and embedding carbon area ratio is 50%～85%.Its step is as follows:
At first, with thick be that 20～30 microns Copper Foil is polished gently with sand paper, with the copper foil surface after the alcohol swab wiping polishing, reach the purpose of removing surface irregularities and its surface oxide layer then, the Copper Foil of handling is carried out cutting, the size that cutting suits the requirements.
Adopting the spark discharge technology, is the conductive electrode A(electrode specification of electric spark working machine with the graphite rod
), with Copper Foil another electrode B as the electric spark working machine, use small-power low-voltage electric spark working machine (model D9120M); Working power 150～200V, operating current 1～2.5A, frequency 50Hz, operating power gently are pressed in conductive electrode A on the Copper Foil at 80W～120W, and slowly mobile, the electrode A translational speed is 0.008～0.05 meter per second.Graphite electrode can be in the copper foil surface point discharge, and guarantor unit's area copper foil surface embedding carbon area ratio does not have securing carbon granule with the hairbrush cleaning then, thereby prepares the lithium ion battery negative copper foil of affluxion body of embedding carbon 50%～85%.
Compared with prior art, advantage of the present invention is:
(1) the present invention moves the special material with carbon element that graphite carbon rod has to be plated to copper foil surface, negative current collector is to be made with extra thin copper foil (20～30 microns) cutting, the copper foil surface carburizing, mainly improve the conductivity of collector, also improved plasticity, roughness, corrosion resistance and the resistance to wear of copper foil surface.
(2) collector of the present invention's preparation more can promote negative current collector at the collection characteristic electron at lithium ion cell electrode place, reduced the internal resistance of lithium ion battery, it is coarse that copper foil surface becomes, increased the collection liquid surface area, the carbon-coating surface have many protruding particles can be fully and negative active core-shell material combine, reduced oxidized possibility simultaneously, increased and recycle number of times.
(3) it is simpler that processing method of the present invention is compared the additive method operation, operates conditions needed still less, and operational environment is more random, and preparation process does not have danger, and is harmless, environmentally safe.
Description of drawings
Fig. 1: the heap(ed) capacity decreasing ratio curve of lithium ion battery;
Fig. 2: the internal resistance size correlation curve of lithium ion battery;
Embodiment
Need to use the sand papering copper foil surface before moving the plating graphite granule, use alcohol swab wiping copper foil surface then, remove surface blot, then dry the processing.
Under lab, adopt average thick 23 microns Copper Foil as electrode B, with graphite rod as conductive electrode A, it is contained on the vibrator of electric spark working machine (D9120M), to polish then and dry the processing after Copper Foil be layered on the smooth smooth metallic conduction plate, and fix, keep copper foil surface smooth, the working machine operating current is 1A, and conductive electrode A gently is pressed on the Copper Foil, and is slowly mobile, translational speed is 0.008 meter per second, come the intensive plating (along the ruler line, move and be plated to the copper foil surface that is invisible to the naked eye, only see pitch black carbon) that moves by plastic flat ruler.Obtain the Copper Foil after the modification that the carbon-coating average thickness is 19 μ m, the embedding carbon area ratio of the copper foil surface of unit are is 63%, with the hairbrush cleaning unnecessary do not have a securing carbon granule, with hair-dryer featheriness surface, be placed in the drying box dry.
The copper foil surface carbon-coating thickness 19 μ m that adopt said method to make, use this Copper Foil and common Copper Foil to prepare lithium ion battery as collector, at material and the mode of operation of all the other preparation lithium ion batteries preparation button secondary lithium battery under the identical situation all.Detect the performance (with lithium ion battery cycle charge-discharge 1000 times, measuring the decreasing ratio of its heap(ed) capacity) of its circulation heap(ed) capacity decreasing ratio after finishing.
Fig. 1 shows, will be significantly less than common lithium ion battery with embedding carbon Copper Foil as the circulation volume decreasing ratio of the lithium ion battery of negative current collector.So the cycle performance of embedding carbon battery is better than common lithium ion battery by contrast, the number of times that can be recycled also can be more than common lithium ion battery.
Need to use the sand papering copper foil surface before moving the plating graphite granule, use alcohol swab wiping copper foil surface then, remove surface blot, then dry the processing.
Indoor at drying experiment, with average thickness be the Copper Foil of 20 μ m as electrode B, with graphite rod as conductive electrode A, it is contained on the vibrator of electric spark working machine, then Copper Foil is layered on the metallic conduction plate, keeps surfacing, the working machine operating current is 1.8A, gently be pressed in electrode on the Copper Foil, slowly mobile, translational speed is 0.02 meter per second, moves plating and (rules along ruler by plastic flat ruler is intensive, move and be plated to the copper foil surface that is invisible to the naked eye, only see pitch black carbon).Obtain the Copper Foil after the modification that the carbon-coating average thickness is 23 μ m, the embedding carbon area ratio of the copper foil surface of unit are is 68%, with alcohol swab wiping copper foil surface gently, removes the surplus carbon particle, is put into the drying box inner drying afterwards.
The copper foil surface carbon-coating thickness 23 μ m that adopt said method to make use this Copper Foil and common Copper Foil to prepare lithium ion battery as negative current collector, all prepare lithium ion battery under the identical situation in the material of all the other preparation lithium ion batteries and mode of operation.Detect its electric conductivity after finishing.
Fig. 2 shows, the lithium ion battery internal resistance of making of embedding carbon Copper Foil is little than common lithium ion battery obviously.So the conductivity of embedding carbon battery is better than common lithium ion battery by contrast, improved the energy utilization rate of lithium ion battery so greatly, reduced power consumption.
Embodiment 3
Need to use the sand papering copper foil surface before moving the plating graphite granule, use alcohol swab wiping copper foil surface then, remove surface blot, then dry the processing.
Indoor at drying experiment, with average thickness be the Copper Foil of 21 μ m as electrode B, with graphite rod as conductive electrode A, it is contained on the vibrator of electric spark working machine, then Copper Foil is layered on the metallic conduction plate, keeps surfacing, the working machine operating current is 2.5A, gently be pressed in electrode on the Copper Foil, slowly mobile, translational speed is 0.04 meter per second, moves plating and (rules along ruler with plastic flat ruler is intensive, move and be plated to the copper foil surface that is invisible to the naked eye, only see pitch black carbon).Obtain the Copper Foil after the modification that the carbon-coating average thickness is 21 μ m, the embedding carbon area ratio of the copper foil surface of unit are is 74%, with alcohol swab wiping copper foil surface gently, removes the surplus carbon particle, is put into oven dry in the drying box afterwards.
The Copper Foil average thickness that uses said method to make is 21 μ m, use this Copper Foil and common Copper Foil to serve as plus plate current-collecting body and make lithium ion battery, under the identical situation of all the other manufacture crafts, the lithium ion battery of preparation, measure its performance and verify the conclusion of embodiment 1, the gained conclusion is the same.
Need to use the sand papering copper foil surface before moving the plating graphite granule, use alcohol swab wiping copper foil surface then, remove surface blot, then dry the processing.
Indoor at drying experiment, with average thickness be the Copper Foil of 20 μ m as electrode B, with graphite rod as conductive electrode A, it is contained on the vibrator of electric spark working machine, then Copper Foil is layered on the metallic conduction plate, keeps surfacing, the working machine operating current is 2.5A, gently be pressed in electrode on the Copper Foil, slowly mobile, translational speed is 0.041 meter per second, moves plating and (rules along ruler with plastic flat ruler is intensive, move and be plated to the copper foil surface that is invisible to the naked eye, only see pitch black carbon).Obtain the Copper Foil after the modification that the carbon-coating average thickness is 15 μ m, the embedding carbon area ratio of the copper foil surface of unit are is 59%, with alcohol swab wiping copper foil surface gently, removes the surplus carbon particle, is put into oven dry in the drying box afterwards.
The Copper Foil average thickness that uses said method to make is 15 μ m, use this Copper Foil and common Copper Foil to serve as plus plate current-collecting body and make lithium ion battery, under the identical situation of all the other manufacture crafts, the lithium ion battery of preparation, measure its performance and verify the conclusion of embodiment 1, the gained conclusion is the same.
Embodiment 5
Need to use the sand papering copper foil surface before moving the plating graphite granule, use alcohol swab wiping copper foil surface then, remove surface blot, then dry the processing.
Indoor at drying experiment, with average thickness be the Copper Foil of 22 μ m as electrode B, with graphite rod as conductive electrode A, it is contained on the vibrator of electric spark working machine, then Copper Foil is layered on the metallic conduction plate, keeps surfacing, the working machine operating current is 2.5A, gently be pressed in electrode on the Copper Foil, slowly mobile, translational speed is 0.018 meter per second, moves plating and (rules along ruler with plastic flat ruler is intensive, move and be plated to the copper foil surface that is invisible to the naked eye, only see pitch black carbon).Obtain the Copper Foil after the modification that the carbon-coating average thickness is 28 μ m, the embedding carbon area ratio of the copper foil surface of unit are is 71%, with alcohol swab wiping copper foil surface gently, removes the surplus carbon particle, is put into oven dry in the drying box afterwards.
The Copper Foil average thickness that uses said method to make is 28 μ m, use this Copper Foil and common Copper Foil to serve as plus plate current-collecting body and make lithium ion battery, under the identical situation of all the other manufacture crafts, the lithium ion battery of preparation, measure its performance and verify the conclusion of embodiment 1, the gained conclusion is the same.
Claims (2)
1. the modification processing method of a lithium ion battery negative copper foil of affluxion body, its step is as follows:
1) at first, with thick be 20～30 microns Copper Foil sand papering, with the copper foil surface after the alcohol swab wiping polishing, reach the purpose of removing surface irregularities and its surface oxide layer then;
2) adopt the spark discharge technology, be the conductive electrode A of electric spark working machine with the graphite rod, with Copper Foil another electrode B as the electric spark working machine, make graphite electrode in the copper foil surface point discharge, unit are copper foil surface embedding carbon area ratio is 50%～85%, do not have securing carbon granule with the hairbrush cleaning then, thereby prepare the lithium ion battery negative copper foil of affluxion body that covers carbon.
2. the modification processing method of a kind of lithium ion battery negative copper foil of affluxion body as claimed in claim 1, it is characterized in that: the working power of electric spark working machine is 150～200V, operating current is 1～2.5A, frequency is 50Hz, operating power is 80W～120W, conductive electrode A gently is pressed on the Copper Foil, and slowly mobile, the electrode A translational speed is 0.008～0.05 meter per second.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104296859A (en) * | 2014-10-15 | 2015-01-21 | 北京交大创新科技中心 | Monitoring device for vibration and temperature state of ultra-high voltage power transformer in operation |
| CN105603372A (en) * | 2015-12-22 | 2016-05-25 | 长春吉大科诺科技有限责任公司 | Electromagnetic drive type graphite inlaying probe adopting arc sputtering |
| CN106129418A (en) * | 2016-08-24 | 2016-11-16 | 江西丰日电源有限公司 | A kind of cathode of lithium battery collector edge carbon device and edge carbon technique thereof |
| CN107505573A (en) * | 2017-07-28 | 2017-12-22 | 郑州比克电池有限公司 | A kind of method for differentiating lithium battery interior negative plate and dropping off |
| CN114752884A (en) * | 2022-04-12 | 2022-07-15 | 广东嘉元科技股份有限公司 | Lithium ion battery modified alloy copper foil test device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007116244A2 (en) * | 2005-06-25 | 2007-10-18 | Elena Shembel | Method of fabricating electrodes with low contact resistance for batteries and double-layer capacitors |
| CN101728537A (en) * | 2008-10-24 | 2010-06-09 | 索尼株式会社 | Anode current collector, anode, and secondary battery |
-
2013
- 2013-03-06 CN CN2013100715512A patent/CN103199261A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007116244A2 (en) * | 2005-06-25 | 2007-10-18 | Elena Shembel | Method of fabricating electrodes with low contact resistance for batteries and double-layer capacitors |
| CN101728537A (en) * | 2008-10-24 | 2010-06-09 | 索尼株式会社 | Anode current collector, anode, and secondary battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104296859A (en) * | 2014-10-15 | 2015-01-21 | 北京交大创新科技中心 | Monitoring device for vibration and temperature state of ultra-high voltage power transformer in operation |
| CN105603372A (en) * | 2015-12-22 | 2016-05-25 | 长春吉大科诺科技有限责任公司 | Electromagnetic drive type graphite inlaying probe adopting arc sputtering |
| CN105603372B (en) * | 2015-12-22 | 2018-03-27 | 长春吉大科诺科技有限责任公司 | Probe is inlayed in the sputtering of electromagnetic drive type graphite arc |
| CN106129418A (en) * | 2016-08-24 | 2016-11-16 | 江西丰日电源有限公司 | A kind of cathode of lithium battery collector edge carbon device and edge carbon technique thereof |
| CN107505573A (en) * | 2017-07-28 | 2017-12-22 | 郑州比克电池有限公司 | A kind of method for differentiating lithium battery interior negative plate and dropping off |
| CN114752884A (en) * | 2022-04-12 | 2022-07-15 | 广东嘉元科技股份有限公司 | Lithium ion battery modified alloy copper foil test device |
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Application publication date: 20130710 |