CN110808355B - Method for processing micro-nano composite structure copper foil current collector underwater by ultrafast laser - Google Patents
Method for processing micro-nano composite structure copper foil current collector underwater by ultrafast laser Download PDFInfo
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- CN110808355B CN110808355B CN201911086560.2A CN201911086560A CN110808355B CN 110808355 B CN110808355 B CN 110808355B CN 201911086560 A CN201911086560 A CN 201911086560A CN 110808355 B CN110808355 B CN 110808355B
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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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0433—Molding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Abstract
The utility model provides a method of ultrafast laser underwater machining micro-nano composite construction copper foil mass flow body, set up femto second laser system earlier, then with commercial for the lithium ion battery copper foil mass flow body fixed to the processingequipment under water, reuse computer regulation femto second laser instrument and the control unit who shakes the mirror, through repetition frequency and the single pulse energy of adjusting femto second laser instrument output laser, the mirror that shakes is controlled simultaneously and then control laser irradiation time and jump to the speed, the irradiation is on the underwater copper foil mass flow body behind the laser focus, the scanning is accomplished, can once only realize: the copper foil current collector has a pore diameter microstructure, a pore diameter microstructure and different micro-nano composite structures such as a nano-pore structure around the micropores, a pore diameter microstructure and a nano-ripple structure around the micropores, and can be widely applied to the lithium ion battery industry.
Description
Technical Field
The invention belongs to the technical field of laser micro-machining, and particularly relates to a method for machining a micro-nano composite structure copper foil current collector underwater by ultrafast laser.
Background
New energy is always paid much attention from all countries in the world, batteries attract a large number of scientific research personnel as energy storage and output tools, and lithium ion batteries are widely applied to the fields of electronics, communication, energy, traffic, aerospace, military, internet and the like by virtue of the good performances of no memory effect, high energy density, good cycle performance, small self-discharge and the like. With the development of science and technology, people put higher demands on the performance of lithium ion batteries: higher capacity, higher energy density and longer service life.
The copper foil current collector of the lithium ion battery cathode provides a possibility for solving the problems of fast capacity attenuation and poor cycle performance of a high-capacity cathode material lithium ion battery, at present, the current collector is processed by a laser, and the processing method mainly focuses on laser drilling, texture and the like, the processed current collector is mostly thick, and at present, the thick current collector is only researched by experiments and cannot be applied to an actual lithium ion battery. A plurality of related documents with micro-nano composite structures are processed on a current collector copper foil commonly used by a battery by utilizing an ultrafast laser, and the related documents are not reported, and a battery material with the huge potential energy of the current collector with the micro-nano composite structure is not excavated.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for processing a micro-nano composite structure copper foil current collector underwater by ultrafast laser, wherein the micro-nano composite structure can be widely applied to lithium ion batteries.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for processing a micro-nano composite structure copper foil current collector underwater by ultrafast laser comprises the following steps:
1) the femtosecond laser processing system is built, the femtosecond laser system comprises a femtosecond laser 1, the laser output by the femtosecond laser 1 passes through a half wave plate 2, and a beam splitter prism 3 splits the laser beam: one laser beam irradiates a power meter probe 15, the other laser beam sequentially passes through a first reflecting mirror 4, a second reflecting mirror 5 and a small-hole diaphragm 6, passes through a beam expanding lens 7, enters a vibrating lens 8 and is focused by a field lens 9, focused light beams irradiate an underwater processing device 11 fixed on an x, y and z adjustable moving objective table 12, and a femtosecond laser 1, a control unit 10 of the vibrating lens, the power meter probe 15 and a computer 13 are connected;
2) fixing a copper foil 14 of 6-12 μm on an underwater processing device 11;
3) the half-wave plate 2, the beam splitter prism 3 and the power meter probe 15 are combined to detect the laser power, meanwhile, the computer 13 controls the movement speed and the track of the laser through the galvanometer control unit 10, and the aperture diaphragm 6 is used for adjusting the size of a light through hole, so that the beam waist radius of an ablation light spot penetrating through the field lens 9 is 20 microns;
4) the computer 13 is utilized to adjust the output laser wavelength of the femtosecond laser 1 to 1030nm, the repetition frequency to be 1kHz-200kHz, the pulse width to be 240fs and the single pulse energy to be 30-50 muJ;
5) the parameters of the femtosecond laser 1 are controlled by the computer 13, the galvanometer 8 is controlled by the computer 13 to further control the pulse delay time and the track of the laser, the pulse delay time is 1000ms-10000ms, and the corresponding pulse number is calculated through pulse delay and laser repetition frequency, so that the current collector with the micro-nano composite structure is obtained.
The underwater processing device 11 comprises an outer water storage tank 11-1, wherein a lifting threaded column 11-5 is arranged at the bottom of the outer water storage tank 11-1, an inner water storage tank 11-2 is arranged above the lifting threaded column 11-5, a fixed table 11-6 is arranged inside the inner water storage tank 11-2, a copper foil 14 is placed above the fixed table 11-6, a water inlet 11-4 is arranged on the outer side of the bottom of the inner water storage tank 11-2, an adjusting handle 11-3 is arranged on the outer side of the inner water storage tank 11-2, and a lower water level control port 11-7, a middle water level control port 11-8 and an upper water level control port 11-9 are arranged at the upper part of the inner water storage tank 11-2;
the water level control is that external water enters the inner water storage tank 11-2 through the water inlet 11-4, the water level of the inner water storage tank 11-2 continuously rises along with the increase of injected water, the distance test of a water layer from the surface of a copper foil is determined by the switches of the lower water level control port 11-7, the middle water level control port 11-8 and the upper water level control port 11-9, when the water level reaches the set water level, the corresponding switch of the water level control port is in an open state, water higher than the corresponding water level control port flows out of the outer water storage tank 11-1 through the water level control port, and under the condition that the water flow rates of the water level control port and the water inlet 11-4 are the same, the height of the water layer can be ensured to be the required thickness.
By adjusting the repetition frequency of the laser, the laser single pulse energy and the laser irradiation time, copper foil current collectors with different micro-nano composite structures can be obtained.
Compared with the prior art, the invention has the following technical effects:
the invention utilizes a femtosecond laser to process a composite structure which not only has micron-scale micropores but also has nanometer-scale micropores or nanometer ripples on a copper foil, utilizes a current collector processed by the femtosecond laser, and can realize the following steps at one time by adjusting the repetition frequency of the laser, the laser single pulse energy and the laser irradiation time: the current collector can be widely applied to the lithium ion battery industry.
Compared with the prior laser drilling and texture processing method, the method has the advantages that: processing micropores in laser air, wherein the periphery of the micropores does not have structures such as nano ripples, nano micropores and the like with various structures; compared with the processed nanostructure of the texture, the method can process various copper foil current collectors with micron and nano composite structures. In addition, the method is simple to operate and high in processing efficiency.
Drawings
Fig. 1 is a schematic view of a femtosecond laser system according to the present invention.
Fig. 2 is a schematic view of the structure of the underwater processing device of the present invention.
Fig. 3 is a result graph of the micro-nano composite structure current collector in embodiment 1 of the present invention.
Fig. 4 is a result graph of the micro-nano composite structure current collector in embodiment 2 of the present invention.
Fig. 5 is a result graph of the micro-nano composite structure current collector in embodiment 3 of the present invention.
Fig. 6 is a result graph of the micro-nano composite structure current collector in embodiment 4 of the present invention.
Detailed Description
The invention is further illustrated in the following description and drawings and examples.
1) the femtosecond laser processing system is built, the femtosecond laser system comprises a femtosecond laser 1, the laser output by the femtosecond laser 1 passes through a half wave plate 2, and a beam splitter prism 3 splits the laser beam: one laser beam irradiates and is focused with a power meter probe 15, the other laser beam sequentially passes through a first reflector 4, a second reflector 5 and an aperture diaphragm 6, passes through a beam expander 7, enters a vibrating lens 8 and is focused through a field lens 9, focused light beams irradiate on an underwater processing device 11 fixed on an x, y and z adjustable moving objective table 12, a femtosecond laser 1, a control unit 10 of the vibrating lens, the power meter probe 15 and a computer 13 are connected, real-time monitoring of the laser power of the laser beam irradiated on the femtosecond laser beam is realized through the power meter probe 15, and then the power of the other laser beam is deduced;
2) fixing a copper foil 14 with the diameter of 6-12 μm of a commercial lithium ion battery on an underwater processing device 11;
referring to fig. 2, the underwater processing device 11 comprises an outer water storage tank 11-1, wherein a lifting threaded column 11-5 is arranged at the bottom of the outer water storage tank 11-1, an inner water storage tank 11-2 is arranged above the lifting threaded column 11-5, a fixed table 11-6 is arranged inside the inner water storage tank 11-2, a copper foil 14 is placed above the fixed table 11-6, a water inlet 11-4 is arranged on the outer side of the bottom of the inner water storage tank 11-2, an adjusting handle 11-3 is arranged on the outer side of the inner water storage tank 11-2, and a lower water level control port 11-7, a middle water level control port 11-8 and an upper water level control port 11-9 are arranged at the upper part of the inner water storage tank;
the water level control is that external water enters the inner water storage tank 11-2 through the water inlet 11-4, the water level of the inner water storage tank 11-2 continuously rises along with the increase of injected water, the distance test of the water layer from the surface of the copper foil is determined by the switches of the lower water level control port 11-7, the middle water level control port 11-8 and the upper water level control port 11-9, when the water level reaches the set water level, the switch of the corresponding water level control port is in an open state, the water higher than the corresponding water level control port flows out to the outer water storage tank 11-1 through the water level control port, and under the condition that the water flow rates of the water level control port and the water inlet 11-4 are the same, the height of the water layer can be ensured to be the required thickness, and the thickness of the;
3) the half-wave plate 2, the beam splitter prism 3 and the power meter probe 15 are combined to detect the laser power, meanwhile, the computer 13 controls the movement speed and the track of the laser through the galvanometer control unit 10, and the aperture diaphragm 6 is used for adjusting the size of a light through hole, so that the beam waist radius of an ablation light spot penetrating through the field lens 9 is 20 microns;
4) utilizing a computer 13 to adjust the output laser wavelength of the femtosecond laser 1 to 1030nm, the repetition frequency to 1kHz, the pulse width to 240fs and the single-pulse energy to be 30 muJ-50 muJ;
5) the parameters of the femtosecond laser 1 are controlled by the computer 13, the galvanometer 8 is controlled by the computer 13 to further control the pulse delay time and the track of the laser, the pulse delay time is 10000ms, the jump speed is 8000mm/s, and the corresponding pulse number is calculated through the pulse delay and the repetition frequency of the laser, so that the current collector with the micro-nano composite structure is obtained.
The effect of this embodiment: referring to fig. 3, a result graph of the micro-nano composite structure current collector obtained in this example (graph a is a 1000-fold enlarged overall graph, graph b is a 7300-fold enlarged pore wall corrugation, and graph c is an 15000-fold enlarged pore wall corrugation); the resulting structure had 59 micron diameter pores with a pore exit diameter of 44 microns, a pore sidewall with corrugations of about 180nm in width, and a corrugation pitch of about 350 nm; the current collector with a composite structure of micro-scale micropores and nano-scale ripples on the walls of the pores with good quality can be seen in the figure. The radius of lithium ions is 76pm, and the nanometer ripple of micro-nano composite structure pore inner wall provides more depending on storage area for the storage of lithium ions, and this structure extends for three-dimensional structure by two-dimensional planar structure and has improved the specific surface area of mass flow body greatly. The cell coatable area is further increased due to the increase of the specific surface area, thereby coating more active material on the same area.
Example 2: like steps 1) to 3) in example 1, step 4) is: utilizing a computer 13 to adjust the output laser wavelength of the femtosecond laser 1 to 1030nm, the repetition frequency to 2kHz, the pulse width to 240fs and the single-pulse energy to be 30 muJ-50 muJ; step 5) is as follows: the parameters of the femtosecond laser 1 are controlled by the computer 13, and the galvanometer 8 is controlled by the computer 13 to control the pulse delay time and the track of the laser, wherein the pulse delay time is 5000ms, and the jumping speed is 8000 mm/s.
The effect of this embodiment: referring to fig. 4, a result graph of the micro-nano composite structure current collector obtained in the present embodiment (a graph a is a 1000-fold enlarged whole graph, a graph b is a 2000-fold enlarged pore wall corrugation, and a graph c is an 4500-fold enlarged pore wall corrugation); the obtained structure is provided with micropores with the diameter of 51 microns, the diameter of the outlet of each micropore is 41 microns, and micro-nano holes with the diameter of 504 nm-1.3 microns are formed around each micropore; the nanohole is surrounded by a periodic corrugation having a width of about 510 nm. The current collector having a composite structure of micro-pores of micro-scale and nano-pores and nano-corrugations around the pores while having good quality can be seen. The ionic radius of lithium ions is 76pm, and micro-nano holes of 504 nm-1.3 mu m around the micro-nano composite structure holes provide larger space for storing the lithium ions.
Example 3: the same steps as steps 1) to 3) in example 1, and step 4) is: the computer 13 is utilized to adjust the output laser wavelength of the femtosecond laser 1 to 1030nm, the repetition frequency to 3.3kHz, the pulse width to 240fs and the single pulse energy to 30 muJ-50 muJ; step 5) is as follows: the parameters of the femtosecond laser 1 are controlled by the computer 13, and the galvanometer 8 is controlled by the computer 13 to control the pulse delay time and the track of the laser, wherein the pulse delay time is 3000ms, and the jump speed is 8000 mm/s.
The effect of this embodiment: referring to fig. 5, a result graph of the micro-nano composite structure current collector obtained in this embodiment (graph a is a 1000-fold enlarged overall graph, and graph b is a 4000-fold enlarged pore wall corrugation); the obtained structure is provided with micropores with the diameter of 54 microns, the diameter of the outlet of each micropore is 42 microns, and micro-nano holes with the diameter of about 500nm are formed around each micropore; the nanohole is surrounded by a periodic corrugation with a width of about 450 nm. The current collector having a composite structure of micro-pores of micro-scale and nano-pores and nano-corrugations around the pores while having good quality can be seen. The ionic radius of lithium ions is 76pm, and the micro-nano holes of 500nm around the micro-nano composite structure holes provide more spaces for the storage of the lithium ions, so that the capacity is improved.
Example 4: the same steps as steps 1) to 4) in example 1 are carried out, and step 4) is changed to: utilizing a computer 13 to adjust the output laser wavelength of the femtosecond laser 1 to 1030nm, the repetition frequency to 10kHz, the pulse width to 240fs and the single-pulse energy to be 30 muJ-50 muJ; step 5) is changed into: the parameters of the femtosecond laser 1 are controlled by the computer 13, and the galvanometer 8 is controlled by the computer 13 to control the pulse delay time and the track of the laser, wherein the pulse delay time is 1000ms, and the jumping speed is 8000 mm/s.
The effect of this embodiment: referring to fig. 6, a result graph of the micro-nano composite structure current collector obtained in this embodiment (a is a 1000-fold enlarged overall graph, and b is a 4000-fold enlarged pore wall corrugation graph); the resulting structure had micropores of 56 microns in diameter, 45 microns in diameter at the outlet of the micropores, periodic corrugations of approximately 350nm in width around the micropores, and a corrugation pitch of 560 nm. The current collector having a composite structure of micro-scale micro-pores and nano-corrugations around the pores with good quality can be seen. These structures provide more space for coating of lithium ions, which is more advantageous to coat more active materials on the same area of current collector since the nano corrugations having a gully shape have more area than a two-dimensional plane, thereby increasing the capacity of the battery.
Claims (3)
1. A method for processing a micro-nano composite structure copper foil current collector underwater by ultrafast laser is characterized by comprising the following steps:
1) set up femto second laser processing system, femto second laser system includes femto second laser instrument (1), and femto second laser instrument (1) output laser passes through half wave plate (2), and beam splitting is carried out laser to spectral prism (3): one laser beam irradiates a power meter probe (15), the other laser beam sequentially passes through a first reflector (4), a second reflector (5) and an aperture diaphragm (6), then passes through a beam expander (7), enters a vibrating mirror (8), is focused through a field lens (9), focused light rays irradiate on an underwater processing device (11) fixed on an x, y and z adjustable moving objective table (12), and a femtosecond laser (1), a control unit (10) of the vibrating mirror, the power meter probe (15) and a computer (13) are connected;
2) fixing a copper foil (14) of 6-12 mu m on an underwater processing device (11);
3) the laser power is detected by using the combination of the half wave plate (2), the beam splitter prism (3) and the power meter probe (15), simultaneously, the computer (13) controls the movement speed and the track of the laser through the control unit (10) of the galvanometer, and the size of a light through hole is adjusted through the small hole diaphragm (6), so that the beam waist radius of an ablation light spot penetrating through the field lens (9) is 20 mu m;
4) a computer (13) is utilized to adjust the output laser wavelength of the femtosecond laser (1) to be 1030nm, the repetition frequency to be 1kHz-200kHz, the pulse width to be 240fs and the single pulse energy to be 30-50 muJ;
5) the parameters of the femtosecond laser device (1) are controlled by a computer (13), meanwhile, the vibrating mirror (8) is controlled by the computer (13) to further control the pulse delay time and the track of the laser, the pulse delay time is 1000ms-10000ms, and the corresponding pulse number is obtained through pulse delay and laser repetition frequency, so that the current collector with the micro-nano composite structure is obtained.
2. The method for processing the micro-nano composite structure copper foil current collector underwater by the ultrafast laser according to claim 1, wherein the method comprises the following steps: the underwater processing device (11) comprises an outer water storage tank (11-1), a lifting threaded column (11-5) is arranged at the bottom of the outer water storage tank (11-1), an inner water storage tank (11-2) is arranged above the lifting threaded column (11-5), a fixed table (11-6) is arranged inside the inner water storage tank (11-2), a copper foil (14) is placed above the fixed table (11-6), a water inlet (11-4) is arranged on the outer side of the bottom of the inner water storage tank (11-2), an adjusting handle (11-3) is arranged on the outer side of the inner water storage tank (11-2), and a lower water level control port (11-7), a middle water level control port (11-8) and an upper water level control port (11-9) are arranged on the upper portion of the inner water storage tank (11-2;
the water level control is that external water enters the inner water storage tank (11-2) through the water inlet (11-4), the water level of the inner water storage tank (11-2) continuously rises along with the increase of injected water, the distance between the water layer and the surface of the copper foil is tested and is determined through the switches of the lower water level control port (11-7), the middle water level control port (11-8) and the upper water level control port (11-9), when the water level reaches the set water level, the corresponding switch of the water level control port is in an open state, water higher than the corresponding water level control port flows out of the outer water storage tank (11-1) through the water level control port, and the height of the water layer can be ensured to be the required thickness under the condition that the water flow rates of the water level control port and the water inlet (11-4).
3. The method for processing the micro-nano composite structure copper foil current collector underwater by the ultrafast laser according to claim 1, wherein the method comprises the following steps: by adjusting the repetition frequency of the laser, the laser single pulse energy and the laser irradiation time, copper foil current collectors with different micro-nano composite structures can be obtained.
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| CN111673270A (en) * | 2020-06-11 | 2020-09-18 | 西安交通大学 | Method for processing improved oil-gas (oil-water) separation explosion-proof valve by using advanced laser system |
| CN112077439B (en) * | 2020-09-04 | 2021-06-22 | 西安交通大学 | Method for processing three-dimensional current collector of energy storage device by laser multi-frequency optimization combination |
| CN112792006B (en) * | 2020-12-29 | 2022-01-07 | 比亚迪股份有限公司 | Method and equipment for removing pole piece active substances |
| CN112928280B (en) * | 2021-03-10 | 2022-06-07 | 中国科学院金属研究所 | Patterning method of copper foil for lithium metal negative electrode |
| CN116565218A (en) * | 2023-06-06 | 2023-08-08 | 哈尔滨工业大学 | Aluminum current collector with root-shaped structure for lithium battery and preparation method of aluminum current collector |
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| CN108133838B (en) * | 2017-12-21 | 2019-09-17 | 北京理工大学 | A method of fake capacitance electrode is prepared based on femtosecond laser composite anode oxide |
| CN109062281A (en) * | 2018-08-17 | 2018-12-21 | 江苏芯界新能源科技有限公司 | A kind of negative electrode of lithium ion battery substrate and preparation method thereof |
| CN109440125A (en) * | 2018-11-30 | 2019-03-08 | 清华大学 | A kind of stainless base steel electrolysis water catalysis electrode and preparation method thereof |
| CN109877470A (en) * | 2019-03-19 | 2019-06-14 | 东华大学 | A kind of preparation method of lithium ion battery porous copper foil |
| CN110102901A (en) * | 2019-04-30 | 2019-08-09 | 上海工程技术大学 | The ultrafast laser three-dimensional micro-nano texture method on negative electrode of lithium ion battery copper foil current collector surface |
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