CN115275212B - Preparation method of copper-based current collector of anodeless lithium ion battery - Google Patents

Preparation method of copper-based current collector of anodeless lithium ion battery Download PDF

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CN115275212B
CN115275212B CN202210953532.1A CN202210953532A CN115275212B CN 115275212 B CN115275212 B CN 115275212B CN 202210953532 A CN202210953532 A CN 202210953532A CN 115275212 B CN115275212 B CN 115275212B
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copper
current collector
ion battery
lithium ion
based current
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CN115275212A (en
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黄永宪
单承
秦志伟
许双明
谢聿铭
孟祥晨
万龙
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Harbin Institute of Technology
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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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C22C2026/002—Carbon nanotubes
    • 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 invention relates to a preparation method of a copper-based current collector of a non-anode lithium ion battery, which comprises the steps of fully crushing and uniformly dispersing multi-wall carbon nanotubes on all parts of a copper matrix through large plastic deformation treatment, so that the lithium affinity of the current collector is improved, and the multi-wall carbon nanotubes serving as a second phase and a nucleation agent for dynamic recrystallization are used for inhibiting grain boundary migration, so that crystal grains are refined and uniformly distributed, and uniform deposition of lithium is ensured. Finally, the copper-based composite material current collector with excellent electrochemical performance is obtained. The invention can improve the cycle stability of the anodeless lithium ion battery, and the preparation process is environment-friendly and can realize large-scale industrial application.

Description

Preparation method of copper-based current collector of anodeless lithium ion battery
Technical Field
The invention relates to a preparation method of a copper-based current collector of a non-anode lithium ion battery, and belongs to the field of electrochemical energy storage.
Background
The anode-free lithium ion battery has the advantages of high energy density, low cost and the like, and has extremely wide development prospect. Among them, the copper current collector is one of the core components of the anodeless lithium ion battery, and the modification problem of the copper current collector is attracting a great deal of attention because of the non-uniformity of the grain size and the lithium-thinning property thereof, which reduce the battery performance.
Conventional modification means include chemical vapor deposition to grow multi-layer graphene, coating polyethylene oxide film, etc., which have complicated process and high production cost, and delay the formation of lithium dendrite by encapsulating deposited lithium with a coating layer, and the non-uniformity of grain size and lithium repellency of the copper current collector itself are not improved, resulting in unavoidable formation of lithium dendrite at high cycle times. If a current collector with fine and uniform particles and high lithium affinity is prepared, the method has great application value and significance in further improving the performance of the lithium ion battery.
Disclosure of Invention
The invention aims to solve the problem that the non-uniformity of the grain size and the lithium-thinning property of a copper current collector are not improved, so that lithium dendrite is formed under the condition of high cycle times, and further provides a preparation method of the anode-free lithium ion battery copper-based current collector
The technical scheme adopted by the invention for solving the problems is as follows: the preparation method of the copper-based current collector of the anodeless lithium ion battery is realized through the following steps:
step one: weighing multiwall carbon nanotubes and copper powder according to the volume fraction of the multiwall carbon nanotubes of 1-15vol.%, ball milling and taking out to obtain powder A;
step two: carrying out argon-hydrogen mixed gas reduction on the powder A to obtain mixed powder B of pure copper and multi-wall carbon nanotubes;
step three: tabletting the powder B to obtain a blank;
step four: and carrying out large plastic deformation treatment on the blank.
Further, in the first step, the diameter of the multiwall carbon nanotube is 4-50nm, and the length is 1-10 μm.
Further, in the step one, the diameter of the copper powder is in the range of 0.1-50 mu m.
Further, in the ball milling process in the first step, a stainless steel ball milling tank is used, ball milling balls are one or more of zirconia balls, steel balls, agate balls and silicon carbide balls with the diameter of 1-10mm, the balls and the mixed powder are mixed according to any ratio, and the mass ratio of the balls to the mixed powder is 10:1, the rotating speed is 100-500rpm, and the ball milling time is 1-72h.
And further, the third step adopts a cold press molding method for tabletting, the pressure is 2-50MPa, the dwell time is 10-300s, and the diameter of a tabletting mold is 10-30mm.
Furthermore, in the fourth step, the restraint piece adopted in the large plastic deformation treatment is a copper ring with the aperture of 10-30mm, and the diameter of the corresponding pressure head is the same as the aperture of the restraint piece.
Further, in the fourth step, the rotational speed of the blank is 50-6000rpm, the rotational time is 10-3600s, and the axial force is 1-100t when the blank is subjected to large plastic deformation treatment.
The beneficial effects of the invention are as follows: according to the invention, the full combination of the multi-wall carbon nano tube and the copper matrix is realized through the large plastic deformation treatment method, so that the multi-wall carbon nano tube is uniformly dispersed at all positions of the copper matrix, the lithium affinity of the current collector is improved, more lithium nucleation sites are provided, and lithium dendrites are prevented from being formed under high cycle times. Meanwhile, the multi-wall carbon nano tube is also used as a nucleating agent for the second phase and dynamic recrystallization, so that migration of crystal boundaries is effectively inhibited, crystal grains are thinned and uniformly distributed, uniformity of lithium nucleation and deposition is improved, and cycle performance of the anode-free lithium ion battery is improved.
Drawings
FIG. 1 is a schematic diagram of a method for preparing a copper-based current collector of an anodeless lithium ion battery;
FIG. 2 is an XRD contrast pattern of a copper-based current collector and a conventional copper foil;
FIG. 3 is a Raman diagram of a multiwall carbon nanotube, ball-milled powder and a composite current collector during the preparation process;
FIG. 4 is an EBSD diagram of a copper-based current collector;
FIG. 5 is a surface lithium deposition morphology of a ball-milled powder morphology and a copper-based current collector;
FIG. 6 is a graph of the cycling performance of a copper-based current collector cell incorporating multiwall carbon nanotubes;
FIG. 7 is a graph comparing half cell coulombic efficiencies of a copper-based current collector and copper foil;
fig. 8 is a graph of full cell coulombic efficiency versus capacity retention for a copper-based current collector and copper foil.
Detailed Description
The first embodiment is as follows: referring to fig. 1 to 8, the preparation method of the copper-based current collector of the anodeless lithium ion battery according to the present embodiment is implemented by the following steps:
step one: weighing multiwall carbon nanotubes and copper powder according to the volume fraction of the multiwall carbon nanotubes of 1-15vol.%, ball milling and taking out to obtain powder A;
step two: carrying out argon-hydrogen mixed gas reduction on the powder A to obtain mixed powder B of pure copper and multi-wall carbon nanotubes;
step three: tabletting the powder B to obtain a blank;
step four: and carrying out large plastic deformation treatment on the blank.
The copper-based current collector meeting the standard is processed through the steps.
The second embodiment is as follows: referring to fig. 1 to 8, in the first step, the multi-walled carbon nanotubes having a diameter of 4-50nm and a length of 1-10 μm are selected according to the specifications of the copper-based current collector to be processed.
And a third specific embodiment: the present embodiment will be described with reference to fig. 1 to 8, wherein the copper powder in the first step has a particle size of 0.1 to 50 μm and is selected according to the processing requirements.
The specific embodiment IV is as follows: referring to fig. 1 to 8, in the first step, a stainless steel ball milling tank is used in the ball milling process, the ball milling balls are one or a mixture of zirconia balls, steel balls, agate balls and silicon carbide balls with the diameter of 1-10mm, the mass ratio of the milling balls to the mixed powder is 10:1, the rotating speed is 100-500rpm, the ball milling time is 1-72h, and the multiwall carbon nanotubes and the copper powder are crushed to form powder with specified size.
Fifth embodiment: referring to fig. 1 to 8, in the second step, the reduction process is performed by using a quartz boat, and a tube furnace is used for reduction, wherein the hydrogen in the reducing gas accounts for 1-10vol.%, the reduction temperature is 200-800 ℃, and the reduction time is 0.5-4h, and the reduction process is used for reducing copper oxide generated in the ball milling process, so that pure copper is obtained and mixed with the multiwall carbon nanotubes.
Specific embodiment six: in the third step, the cold press molding is performed under a pressure of 2-50MPa and a dwell time of 10-300s, and the diameter of the tabletting mold is 10-30mm, and the copper-based current collector to be processed is changed according to the need, with reference to fig. 1 to 8.
Seventh embodiment: in the fourth step, the mixed powder of copper powder and multiwall carbon nanotubes is extruded through a copper ring, wherein the restraining member used in the large plastic deformation treatment is a copper ring with the aperture of 10-30mm, and the diameter of the corresponding pressing head is the same as the aperture of the restraining member.
Eighth embodiment: referring to fig. 1 to 8, in the fourth step, the rotational speed of the blank is 50-6000rpm, the rotational time is 10-3600s, the axial force is 1-100t, and gas protection measures such as argon inert gas protection, nitrogen protection and the like can be adopted in the cold pressing and the large plastic deformation treatment process to prevent secondary oxidation of the reduced mixed powder.
Examples
The preparation of the copper-based current collector of the non-anode lithium ion battery by using the method is carried out by the following steps:
firstly, weighing multiwall carbon nanotubes and copper powder according to the volume fraction of the multiwall carbon nanotubes of 2vol.%, performing ball milling at the speed of 300rpm for 5 hours, and using stainless steel balls and a ball milling tank, wherein the ball-to-material ratio is 10:1 to obtain powder A;
step two, carrying out argon-hydrogen mixed gas reduction on the powder A, wherein the reduction process is to reduce the powder A for 1h at 400 ℃ by using a tube furnace, the hydrogen content in the reduction gas is 5 vol%, and cooling the reduction gas along with the furnace to obtain mixed powder B of pure copper and multi-wall carbon nanotubes;
step three, tabletting the powder B, wherein the tabletting is to use a cold press molding mode to carry out tabletting on the powder, the pressure is 5MPa, the pressure maintaining time is 30s, the diameter of a tabletting mold is 16mm, and a blank is obtained after tabletting;
and fourthly, performing large plastic deformation treatment on the blank, wherein the large plastic deformation treatment uses a copper ring with the aperture of 16mm as a constraint, a large plastic deformation treatment schematic diagram is shown in figure 1, the large plastic deformation treatment rotating speed is 1000rpm, the time is 30s, the axial force is 20t, and argon is used as shielding gas.
The preparation of the copper-based current collector of the non-anode lithium ion battery is carried out by using pure copper powder, and the preparation is carried out by the following steps:
step one, tabletting pure copper powder, wherein the pressure is 5MPa, the dwell time is 30s, and the diameter of a tabletting mould is 16mm;
and secondly, carrying out large plastic deformation treatment on the pressed sheet, using a copper ring with the aperture of 16mm as constraint, rotating at 1000rpm for 30s, and using argon as shielding gas with the axial force of 20 t.
Compared with the two methods, XRD data after large plastic deformation treatment are shown in figure 2, the number and the angle positions of diffraction peaks of a copper-based composite material added with the multiwall carbon nano tube and a pure copper material not added with the multiwall carbon nano tube are consistent with those of standard cards of pure copper, and the amplified peak shapes are in split shapes and coincide with the face-centered cubic structure of copper. As shown in fig. 3, the behavior of the multiwall carbon nanotubes is changed during the ball milling and the large plastic deformation process, the damage degree of the multiwall carbon nanotubes is increased as the processing process proceeds, the graphitization degree is reduced, and the multiwall carbon nanotubes are uniformly distributed in the current collector, which can provide more defects to facilitate uniform deposition of lithium. As shown in FIG. 4, the EBSD of the prepared copper-based composite material, pure copper material and copper foil has average grain sizes of 1.93 μm, 4.05 μm and 40.46 μm respectively, and the grain size distribution of the copper-based composite material is more uniform. As shown in fig. 5, the lithium deposition is performed on the surfaces of the three material current collectors to compare the morphology, and it can be found that the lithium deposition is uneven on the surfaces of the copper foil and the pure copper material current collector, and more unconnected areas exist. The copper-based composite material current collector added with the multiwall carbon nanotubes is compared, the surface lithium deposition is very uniform, and all areas are connected.
As shown in FIG. 6, the assembled half cell of the copper-based composite material prepared by the large plastic deformation treatment can be stably circulated for 1000 hours at 1mA/cm2 without generating a significant polarization phenomenon. As shown in fig. 7, in order to explore the electrochemical performance difference of the prepared copper-based composite current collector, pure copper current collector and copper foil, half cells were assembled, the current density was 1mA/cm2, the copper foil was circulated for 200 weeks, the pure copper current collector was destroyed after being circulated for 260 weeks, and as a control, the copper-based composite current collector added with multi-walled carbon nanotubes remained at more than 95% in coulomb efficiency after being circulated for 500 weeks, and the cycle performance was excellent. As shown in fig. 8, the full cell was assembled using lithium iron phosphate as the positive electrode, the rate was 0.5C, the capacity of the copper foil and the pure copper current collector was rapidly reduced, the capacity retention rate was less than 60% after 75 weeks of circulation, and the capacity remained by 75% or more after 75 weeks of circulation by using the copper-based composite material containing the multiwall carbon nanotubes as a control, which was excellent in cycle performance.
The present invention is not limited to the preferred embodiments, but is capable of modification and variation in detail, and other embodiments, such as those described above, of making various modifications and equivalents will fall within the spirit and scope of the present invention.

Claims (7)

1. A preparation method of a copper-based current collector of a non-anode lithium ion battery is characterized by comprising the following steps: the preparation method of the copper-based current collector of the anodeless lithium ion battery is realized through the following steps:
step one: weighing multiwall carbon nanotubes and copper powder according to the volume fraction of the multiwall carbon nanotubes of 1-15vol.%, ball milling and taking out to obtain powder A;
step two: carrying out argon-hydrogen mixed gas reduction on the powder A to obtain mixed powder B of pure copper and multi-wall carbon nanotubes;
step three: tabletting the powder B to obtain a blank;
step four: carrying out large plastic deformation treatment on the blank;
wherein, the rotational speed of the blank in the fourth step is 50-6000rpm, the rotational time is 10-3600s, and the axial force is 1-100t when the blank is subjected to large plastic deformation treatment.
2. The method for preparing the copper-based current collector of the anodeless lithium ion battery, according to claim 1, is characterized in that: in the first step, the diameter of the multiwall carbon nanotube is 4-50nm, and the length is 1-10 mu m.
3. The method for preparing the copper-based current collector of the anodeless lithium ion battery according to claim 2, which is characterized in that: the particle size of the copper powder in the first step is 0.1-50 mu m.
4. The method for preparing the copper-based current collector of the anodeless lithium ion battery according to claim 3, wherein the method comprises the following steps: in the first step, a stainless steel ball milling tank is used in the ball milling process, wherein the ball milling balls are one or more of zirconia balls, steel balls, agate balls and silicon carbide balls with the diameter of 1-10mm, and the mass ratio of the grinding balls to the mixed powder is 10:1, the rotating speed is 100-500rpm, and the ball milling time is 1-72h.
5. The method for preparing the copper-based current collector of the anodeless lithium ion battery, according to claim 1, is characterized in that: in the second step, the reduction process adopts a quartz boat, and a tube furnace is used for reduction, wherein the hydrogen in the reduction gas accounts for 1-10vol.%, the reduction temperature is 200-800 ℃, and the reduction time is 0.5-4h.
6. The method for preparing the copper-based current collector of the anodeless lithium ion battery, according to claim 1, is characterized in that: and step three, the tabletting mode is cold press molding, the pressure is 2-50MPa, the dwell time is 10-300s, and the diameter of a tabletting mold is 10-30mm.
7. The method for preparing the copper-based current collector of the anodeless lithium ion battery, according to claim 1, is characterized in that: and step four, the restraint piece adopted in the large plastic deformation treatment is a copper ring with the aperture of 10-30mm, and the diameter of the corresponding pressure head is the same as the aperture of the restraint piece.
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