CN114628686A - Production method of porous copper micron hollow sphere current collector - Google Patents
Production method of porous copper micron hollow sphere current collector Download PDFInfo
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- CN114628686A CN114628686A CN202210236415.3A CN202210236415A CN114628686A CN 114628686 A CN114628686 A CN 114628686A CN 202210236415 A CN202210236415 A CN 202210236415A CN 114628686 A CN114628686 A CN 114628686A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
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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
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
Abstract
The invention provides a production method of a porous copper micron hollow sphere current collector, and particularly relates to a preparation method of a porous copper micron hollow sphere and a preparation method of a current collector. The preparation method of the porous copper micron hollow sphere is a wet chemical method, and specifically, a zinc micron sphere or a zinc oxide micron sphere is used as a self-sacrifice template to obtain a porous hollow structure. The preparation method of the current collector is a physical method, and specifically adopts liquid phase coating, high-temperature sintering, spin coating, screen printing, 3D printing and the like. The preparation method of the micron-sized porous copper micron hollow sphere provided by the invention enables lithium metal to be fully contained in the porous copper micron hollow sphere, and the load capacity of the lithium metal is increased. The copper micron hollow sphere current collector with the three-dimensional porous structure obtained by the method greatly reduces the quality of the three-dimensional copper current collector, releases stress in the lithium deposition process, can enable lithium metal to be contained in the pores of the porous copper micron hollow sphere, continuously increases the loading capacity of the lithium metal, and effectively inhibits the growth of lithium dendrites.
Description
Technical Field
The invention relates to a production method of a porous copper micron hollow sphere current collector, and belongs to the technical field of energy storage batteries.
Background
The lithium copper alloy is one of the most ideal current collector materials of the lithium metal negative electrode at present. The traditional negative current collector is a copper foil, but the planar copper foil as the negative current collector is easy to generate larger local current due to small specific surface area, so that the probability of lithium dendrite generation in the battery cycle process is increased, the battery short circuit is caused, the density of copper is large, and the current collector is an inactive substance which does not contribute to the energy of the battery, and the service life, the safety and the energy density of the lithium battery can be influenced. Even though the three-dimensional porous copper current collector can solve the key problems of Lithium Metal Batteries (LMBs), the current collector is made of copper (8.960g cm)-3) The density is much higher than that of lithium (0.534g cm)-3) The copper-based three-dimensional copper-based current collector is an inactive material, does not provide any capacity, occupies a certain volume and mass, and seriously hinders the improvement of the specific capacity and the specific volume capacity of the battery, so that the problem that the three-dimensional copper-based current collector needs to be solved in the application of a future energy storage device is solved urgently. By passingThe novel current collector is constructed, so that the deposition mode of metal lithium can be changed, and the current and lithium ions are uniformly distributed on the surface of the negative electrode. The current collector with the three-dimensional structure can increase the specific surface area of the current collector and reduce the current density, and meanwhile, the three-dimensional structure can also eliminate the volume change of the metal lithium in the stripping/deposition process so as to achieve the purpose of eliminating lithium dendrites.
In view of the above, it is necessary to provide a method for producing a porous copper micro hollow sphere current collector to solve the above problems.
Disclosure of Invention
The invention aims to provide a production method of a porous copper micron hollow sphere current collector, which is used for reducing the potential safety hazard of a battery, prolonging the service life and stability of the battery, improving the energy density of a lithium metal battery, simplifying the production operation and reducing the pollution, energy consumption and cost.
In order to achieve the aim, the invention provides a production method of a porous copper micron hollow sphere current collector, which mainly comprises the following steps:
step 1, taking a complex of zinc powder or zinc oxide powder and copper, and dissolving the complex of copper in a solvent to obtain a mixed solution;
step 2, placing the mixed solution in an environment of 160-180 ℃ for displacement reaction for 2-6 h;
step 3, annealing at 250-300 ℃ after the replacement reaction,
step 4, after etching in an etching solvent, carrying out vacuum drying to obtain porous copper micron hollow sphere powder with a regular shape;
step 5, grinding and mixing the porous copper micron hollow sphere powder obtained in the step 4 and a binder according to the mass ratio of 20:1, and dropwise adding a trace amount of organic solution to fully infiltrate the porous copper micron hollow sphere powder;
step 6, stirring for 2-4 hours at the speed of 600-800 r/min to obtain uniformly mixed slurry;
step 7, combining the porous copper micron hollow sphere with the copper foil by liquid phase coating, high-temperature sintering, spin coating, screen printing and 3D printing methods;
and 8, drying under the conditions of vacuum and 25-60 ℃ to obtain the porous copper micron hollow sphere current collector.
As a further improvement of the invention, in step 1, the reactant zinc powder or zinc oxide powder is micron-grade reactant zinc powder or zinc oxide powder.
As a further improvement of the invention, in step 1, the copper complex is copper acetylacetonate, copper tetraammine sulfate or copper tetraammine hydroxide.
As a further improvement of the present invention, in step 1, the solvent for dissolving the copper complex is ethylene glycol or methanol.
As a further improvement of the present invention, in step 3, the method of the displacement reaction is a solvothermal method or an oil bath heating method.
As a further improvement of the invention, in step 4, the etching solvent is 5 wt% of dilute hydrochloric acid or dilute formic acid.
As a further development of the invention, the etching time is from 0.5 to 6 hours, preferably 0.5 hour.
As a further improvement of the invention, in step 7, the binder is at least one of polyvinylidene fluoride, polytetrafluoroethylene, acrylic resin emulsion and sodium carboxymethyl cellulose; the solvent is a nonpolar or weak polar organic solvent, and the organic solvent is at least one of toluene, normal hexane, pentane, N-methyl pyrrolidone and styrene butadiene rubber.
As a further improvement of the present invention, in step 7, the combining manner is coating, spraying, spin coating or 3D printing.
As a further improvement of the invention, the drying time in the step 8 is 0.5 to 24 hours, preferably 2 hours.
The invention has the beneficial effects that: according to the production method of the porous copper micron hollow sphere current collector, the obtained three-dimensional porous copper micron hollow sphere current collector can increase the specific surface area of the current collector, reduce the current density, reduce the internal contact resistance of copper and lithium, effectively inhibit the formation of dendritic crystal lithium, prevent the safety problems of short circuit and the like caused in the circulation process of the battery, greatly improve the safety, stability and service life of the battery, and the porous copper micron hollow sphere is light in weight, can contain more lithium, reduces the mass of inactive substances, improves the energy density of the battery, simplifies the production operation, and reduces pollution, energy consumption and cost.
Drawings
FIG. 1 is a flow chart of the preparation of the porous copper micron hollow sphere of the present invention.
FIG. 2 is a flow chart of the preparation of the porous copper micron hollow sphere collective flow in the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
As shown in fig. 1, the invention discloses a production method of a porous copper micron hollow sphere current collector, which has important theoretical guiding significance for reducing the mass of inactive substances of the current collector, releasing stress generated in the lithium deposition process, inhibiting the growth of lithium dendrites and improving the safety, the cyclicity and the energy density of a lithium metal battery, and has important practical significance for promoting the commercialization of the lithium metal battery with high safety, high stability and long cycle capacity.
The production method mainly comprises the following steps:
step 1, taking a complex of zinc powder or zinc oxide powder and copper, and dissolving the complex of copper in a solvent such as ethylene glycol or methanol to obtain a mixed solution;
step 2, placing the mixed solution in an environment of 160-180 ℃ for displacement reaction for 2-6 h;
step 3, annealing at 250-300 ℃ after the replacement reaction;
step 4, etching in 5 wt% dilute hydrochloric acid or dilute formic acid, and then drying in vacuum to obtain porous copper micron hollow sphere powder with regular shape;
step 5, mixing the porous copper micron hollow sphere powder obtained in the step 4 with a binder according to a mass ratio of 20:1, and dropwise adding a trace amount of organic solution to fully infiltrate the porous copper micron hollow sphere powder;
step 6, stirring for 2-4 hours at the speed of 600-800 r/min to obtain uniformly mixed slurry;
step 7, combining the porous copper micron hollow sphere with the copper foil by liquid phase coating, high-temperature sintering, spin coating, screen printing and 3D printing methods;
and 8, drying under the conditions of vacuum and 25-60 ℃ to obtain the porous copper micron hollow sphere current collector.
The following detailed description will be made in conjunction with various embodiments.
Example 1
One kilogram of commercial 5 micron zinc powder, 0.5 kilogram of copper acetylacetonate and 9.5 kilograms of ethylene glycol are taken, the copper acetylacetonate is dissolved in the ethylene glycol, and the zinc powder is added to obtain a mixed solution. Reacting the solution at 160 ℃ for 4 hours by using an oil bath method, annealing at 250 ℃ after the replacement reaction is finished, and etching for 30min by using a dilute hydrochloric acid solution with the volume fraction of 5% to obtain porous copper micron hollow sphere powder with regular shape.
And (3) respectively cleaning 1 kg of porous copper micron hollow sphere powder with ultrapure water, ethanol and acetone for three times to remove impurities such as grease on the surface, and drying the cleaned product in vacuum for 6 hours to obtain the treated hollow copper particles.
And adding 1 kg of treated porous copper micron hollow sphere powder into a glass container, adding 100 g of PVDF as a binder and 0.5 kg of NMP as a solvent, and uniformly stirring to obtain porous copper micron hollow sphere powder slurry for later use, wherein the whole stirring temperature is 25 ℃.
And uniformly coating the mixed slurry on a copper foil by selecting a scraper with the specification of 100 micrometers, wherein the surface area of the copper foil is 1 square meter, and thus obtaining the coated pole piece. And drying the coated pole piece (at 60 ℃) under the protection of argon atmosphere to obtain the porous copper micron hollow sphere current collector pole piece. And then, forming the porous copper micron hollow sphere current collector pole piece punching sheet according to the size of the battery pole piece.
The selected battery model is a 2032 type button battery, so the diameter of the pole piece is set to be 12 mm, and the obtained pole piece is a porous copper micron hollow sphere current collector. The porous copper micron hollow sphere current collector is assembled in a symmetrical battery to test the voltage hysteresis condition under large current, and the test value is 10mV, which proves that the porous copper micron hollow sphere current collector has good stability.
Example 2
One kilogram of commercial 5-micron zinc oxide powder, 0.5 kilogram of copper acetylacetonate and 9.5 kilograms of ethylene glycol are taken, the copper acetylacetonate is dissolved in the ethylene glycol, and the zinc oxide powder is added to obtain a mixed solution. Reacting the solution at 160 ℃ for 4h by using an oil bath method, annealing at 250 ℃ after the displacement reaction is finished, and etching with a dilute hydrochloric acid solution with the volume fraction of 5% for 30min to obtain porous copper micron hollow sphere powder with regular shape.
And (3) respectively cleaning 1 kg of porous copper micron hollow sphere powder with ultrapure water, ethanol and acetone for three times to remove impurities such as grease on the surface, and drying the cleaned product in vacuum for 6 hours to obtain the treated porous copper micron hollow sphere powder.
And (3) adding 1 kg of the treated porous copper micron hollow sphere powder into a glass container, adding 100 g of PVDF as a binder and 0.5 kg of NMP as a solvent, and uniformly stirring to obtain a porous copper micron hollow sphere powder slurry for later use, wherein the whole stirring temperature is 25 ℃.
And uniformly coating the mixed slurry on a copper foil by selecting a scraper with the specification of 100 micrometers, wherein the surface area of the copper foil is 1 square meter, and thus obtaining the coated pole piece. And drying the coated pole piece under the protection of argon (at 60 ℃) to obtain the porous copper micron hollow sphere current collector. And then, forming the porous copper micron hollow sphere current collector pole piece punching sheet according to the size of the battery pole piece.
The selected battery model is a 2032 type button battery, so the diameter of the pole piece is set to be 12 mm, and the obtained pole piece is a porous copper micron hollow sphere current collector. The porous copper micron hollow sphere current collector is assembled in a symmetrical battery to test the voltage hysteresis condition under large current, and the test value is 15mV, which proves that the porous copper micron hollow sphere current collector has good stability.
Example 3
One kilogram of commercial 5-micron zinc powder, 0.5 kilogram of copper tetramine sulfate and 9.5 kilograms of ethylene glycol are taken, the copper tetramine sulfate is dissolved in the ethylene glycol, and the zinc powder is added to obtain a mixed solution. Reacting the solution at 160 ℃ for 4h by using an oil bath method, annealing at 250 ℃ after the displacement reaction is finished, and etching with a dilute hydrochloric acid solution with the volume fraction of 5% for 30min to obtain porous copper micron hollow sphere powder with regular shape.
And (3) respectively cleaning 1 kg of porous copper micron hollow sphere powder with ultrapure water, ethanol and acetone for three times to remove impurities such as grease on the surface, and drying the cleaned product in vacuum for 6 hours to obtain the treated hollow copper particles.
And adding 1 kg of treated porous copper micron hollow sphere powder into a glass container, adding 100 g of PVDF as a binder and 0.5 kg of NMP as a solvent, and uniformly stirring to obtain porous copper micron hollow sphere slurry for later use, wherein the whole stirring temperature is 25 ℃.
And uniformly coating the mixed slurry on a copper foil by selecting a scraper with the specification of 100 micrometers, wherein the surface area of the copper foil is 1 square meter, and thus obtaining the coated pole piece. And drying the coated pole piece under the protection of argon (at 60 ℃) to obtain the porous copper micron hollow sphere current collector. And then, forming the porous copper micron hollow sphere current collector pole piece punching sheet according to the size of the battery pole piece.
The selected battery model is a 2032 type button battery, so the diameter of the pole piece is set to be 12 mm, and the obtained pole piece is a porous copper micron hollow sphere current collector. The porous copper micron hollow sphere current collector is assembled in a symmetrical battery to test the voltage hysteresis condition under large current, and the test value is 15mV, which proves that the porous copper micron hollow sphere current collector has good stability.
Example 4
One kilogram of commercial 5-micron zinc powder, 0.5 kilogram of tetraammine copper hydroxide and 9.5 kilograms of ethylene glycol are taken, the tetraammine copper hydroxide is dissolved in the ethylene glycol, and the zinc powder is added to obtain a mixed solution. Reacting the solution at 160 ℃ for 4h by using an oil bath method, annealing at 250 ℃ after the displacement reaction is finished, and etching with a dilute hydrochloric acid solution with the volume fraction of 5% for 30min to obtain porous copper micron hollow sphere powder with regular shape.
And (3) respectively cleaning 1 kg of porous copper micron hollow sphere powder with ultrapure water, ethanol and acetone for three times to remove impurities such as grease on the surface, and drying the cleaned product in vacuum for 6 hours to obtain the treated porous copper micron hollow sphere powder.
And adding 1 kg of treated porous copper micron hollow sphere powder into a glass container, adding 100 g of PVDF as a binder and 0.5 kg of NMP as a solvent, and uniformly stirring to obtain porous copper micron hollow sphere slurry for later use, wherein the whole stirring temperature is 25 ℃.
And uniformly coating the mixed slurry on a copper foil by selecting a scraper with the specification of 100 micrometers, wherein the surface area of the copper foil is 1 square meter, and thus obtaining the coated pole piece. And drying the coated pole piece under the protection of argon (at 60 ℃) to obtain the porous copper micron hollow sphere current collector. And then, forming the porous copper micron hollow sphere current collector pole piece punching sheet according to the size of the battery pole piece.
The selected battery model is a 2032 type button battery, so the diameter of the pole piece is set to be 12 mm, and the obtained pole piece is a porous copper micron hollow sphere current collector negative electrode. The porous copper micron hollow sphere current collector negative battery is assembled in a symmetrical battery to test the voltage hysteresis condition under large current, and the test value is 18mV, which proves that the stability of the porous copper micron hollow sphere current collector is good.
Example 5
One kilogram of commercial 5 micron zinc powder, 0.5 kilogram of copper acetylacetonate and 9.5 kilograms of ethylene glycol are taken, the copper acetylacetonate is dissolved in the ethylene glycol, and the zinc powder is added to obtain a mixed solution. Reacting the solution at 160 ℃ for 4h by using an oil bath method, annealing at 250 ℃ after the displacement reaction is finished, and etching with a dilute hydrochloric acid solution with the volume fraction of 5% for 30min to obtain porous copper micron hollow sphere powder with regular shape.
And (3) respectively cleaning 1 kg of porous copper micron hollow sphere powder with ultrapure water, ethanol and acetone for three times to remove impurities such as grease on the surface, and drying the cleaned product in vacuum for 6 hours to obtain the treated porous copper micron hollow sphere powder.
And adding 1 kg of treated porous copper micron hollow sphere powder into a glass container, adding 100 g of CMC serving as a binder and 0.5 kg of SBR serving as a solvent, and uniformly stirring to obtain porous copper micron hollow sphere slurry for later use, wherein the whole stirring temperature is 25 ℃.
And uniformly coating the mixed slurry on a copper foil by selecting a scraper with the specification of 100 micrometers, wherein the surface area of the copper foil is 1 square meter, and thus obtaining the coated pole piece. And drying the coated pole piece under the protection of argon (at 60 ℃) to obtain the porous copper micron hollow sphere current collector. And then, forming the porous copper micron hollow sphere current collector pole piece punching sheet according to the size of the battery pole piece.
The selected battery model is a 2032 type button battery, so the diameter of the pole piece is set to be 12 mm, and the obtained pole piece is a porous copper micron hollow sphere current collector. The porous copper micron hollow sphere current collector negative electrode is assembled in a symmetrical battery to test the voltage hysteresis condition under large current, and the test value is 20mV, which proves that the porous copper micron hollow sphere current collector has good stability.
Example 6
One kilogram of commercial 5 micron zinc powder, 0.5 kilogram of copper acetylacetonate and 9.5 kilograms of ethylene glycol are taken, the copper acetylacetonate is dissolved in the ethylene glycol, and the zinc powder is added to obtain a mixed solution. Reacting the solution at 160 ℃ for 4 hours by using an oil bath method, annealing at 250 ℃ after the replacement reaction is finished, and etching for 30min by using a dilute hydrochloric acid solution with the volume fraction of 5% to obtain porous copper micron hollow sphere powder with regular shape.
And (3) respectively cleaning 1 kg of porous copper micron hollow sphere powder with ultrapure water, ethanol and acetone for three times to remove impurities such as grease on the surface, and drying the cleaned product in vacuum for 6 hours to obtain the treated porous copper micron hollow sphere powder.
And adding 1 kg of treated porous copper micron hollow sphere powder into a glass container, adding 100 g of PTFE as a binder and 0.5 kg of NMP as a solvent, and uniformly stirring to obtain porous copper micron hollow sphere slurry for later use, wherein the whole stirring temperature is 25 ℃.
And uniformly coating the mixed slurry on a copper foil by selecting a scraper with the specification of 100 micrometers, wherein the surface area of the copper foil is 1 square meter, and thus obtaining the coated pole piece. And drying the coated pole piece under the protection of argon (at 60 ℃) to obtain the porous copper micron hollow sphere current collector. And then, forming the porous copper micron hollow sphere current collector pole piece punching sheet according to the size of the battery pole piece.
The selected battery model is a 2032 type button battery, so the diameter of the pole piece is set to be 12 mm, and the obtained pole piece is a hollow copper current collector negative electrode. The porous copper micron hollow sphere current collector is assembled in a symmetrical battery to test the voltage hysteresis condition under large current, and the test value is 18mV, which proves that the porous copper micron hollow sphere current collector has good negative stability.
Example 7
One kilogram of commercial 5 micron zinc powder, 0.5 kilogram of copper acetylacetonate and 9.5 kilograms of ethylene glycol are taken, the copper acetylacetonate is dissolved in the ethylene glycol, and the zinc powder is added to obtain a mixed solution. Reacting the solution at 160 ℃ for 4h by using an oil bath method, annealing at 250 ℃ after the displacement reaction is finished, and etching with a dilute hydrochloric acid solution with the volume fraction of 5% for 30min to obtain porous copper micron hollow sphere powder with regular shape.
And (3) respectively cleaning 1 kg of porous copper micron hollow sphere powder with ultrapure water, ethanol and acetone for three times to remove impurities such as grease on the surface, and drying the cleaned product in vacuum for 6 hours to obtain the treated porous copper micron hollow sphere powder.
And (3) adding 1 kg of treated porous copper micron hollow sphere powder into a glass container, adding 100 g of PVDF as a binder and 0.5 kg of toluene as a solvent, and uniformly stirring to obtain a porous copper micron hollow sphere slurry for later use, wherein the whole stirring temperature is 25 ℃.
And uniformly coating the mixed slurry on a copper foil by selecting a scraper with the specification of 100 micrometers, wherein the surface area of the copper foil is 1 square meter, and thus obtaining the coated pole piece. And drying the coated pole piece under the protection of argon (at 60 ℃) to obtain the porous copper micron hollow sphere current collector. And then, forming the porous copper micron hollow sphere current collector pole piece punching sheet according to the size of the battery pole piece.
The selected battery model is a 2032 type button battery, so the diameter of the pole piece is set to be 12 mm, and the obtained pole piece is a porous copper micron hollow sphere current collector. The porous copper micron hollow sphere current collector is assembled in a symmetrical battery to test the voltage hysteresis condition under large current, and the test value is 22mV, which proves that the porous copper micron hollow sphere current collector has good stability.
Example 8
One kilogram of commercial 5 micron zinc powder, 0.5 kilogram of copper acetylacetonate and 9.5 kilograms of ethylene glycol are taken, the copper acetylacetonate is dissolved in the ethylene glycol, and the zinc powder is added to obtain a mixed solution. Reacting the solution at 160 ℃ for 4h by using an oil bath method, annealing at 250 ℃ after the displacement reaction is finished, and etching with a dilute hydrochloric acid solution with the volume fraction of 5% for 30min to obtain the porous copper micron hollow sphere with a regular shape.
And (3) respectively cleaning 1 kg of hollow copper by adopting ultrapure water, ethanol and acetone for three times to remove impurities such as grease on the surface, and drying the cleaned product in vacuum for 6 hours to obtain the treated porous copper micron hollow sphere powder.
And adding 1 kg of treated porous copper micron hollow sphere powder into a glass container, adding 100 g of PTFE as a binder and 0.5 kg of NMP as a solvent, and uniformly stirring to obtain porous copper micron hollow sphere slurry for later use, wherein the whole stirring temperature is 25 ℃.
And uniformly coating the mixed slurry on a copper foil by selecting a scraper with the specification of 100 micrometers, wherein the surface area of the copper foil is 1 square meter, and thus obtaining the coated pole piece. And drying the coated pole piece under the protection of argon (at 60 ℃) to obtain the porous copper micron hollow sphere current collector. And then, forming the porous copper micron hollow sphere current collector pole piece punching sheet according to the size of the battery pole piece.
The selected battery model is a 2032 type button battery, so the diameter of the pole piece is set to be 12 mm, and the obtained pole piece is a porous copper micron hollow sphere current collector. The hollow copper current collector is assembled in a symmetrical battery to test the voltage hysteresis condition under large current, and the test value is 16mV, which proves that the porous copper micron hollow sphere current collector has good stability.
Example 9
One kilogram of commercial 5 micron zinc powder, 0.5 kilogram of copper acetylacetonate and 9.5 kilograms of ethylene glycol are taken, the copper acetylacetonate is dissolved in the ethylene glycol, and the zinc powder is added to obtain a mixed solution. Reacting the solution at 160 ℃ for 4h by using an oil bath method, annealing at 250 ℃ after the displacement reaction is finished, and etching with a dilute hydrochloric acid solution with the volume fraction of 5% for 30min to obtain porous copper micron hollow sphere powder with regular shape.
And (3) respectively cleaning 1 kg of porous copper micron hollow sphere powder with ultrapure water, ethanol and acetone for three times to remove impurities such as grease on the surface, and drying the cleaned product in vacuum for 6 hours to obtain the treated porous copper micron hollow sphere powder.
And (3) adding 1 kg of treated porous copper micron hollow sphere powder into a glass container, adding 100 g of PTFE (polytetrafluoroethylene) serving as a binder and 0.5 kg of toluene serving as a solvent, and uniformly stirring to obtain a slurry of the porous copper micron hollow sphere for later use, wherein the whole stirring temperature is 25 ℃.
And uniformly coating the mixed slurry on a copper foil by selecting a scraper with the specification of 100 micrometers, wherein the surface area of the copper foil is 1 square meter, and thus obtaining the coated pole piece. And drying the coated pole piece under the protection of argon (at 60 ℃) to obtain the porous copper micron hollow sphere current collector. And then, forming the porous copper micron hollow sphere current collector pole piece punching sheet according to the size of the battery pole piece.
The selected battery model is a 2032 type button battery, so the diameter of the pole piece is set to be 12 mm, and the obtained pole piece is a porous copper micron hollow sphere current collector. The porous copper micron hollow sphere current collector is assembled in a symmetrical battery to test the voltage hysteresis condition under large current, and the test value is 20mV, which proves that the porous copper micron hollow sphere current collector has good stability.
Example 10
One kilogram of commercial 5 micron zinc powder, 0.5 kilogram of copper acetylacetonate and 9.5 kilograms of ethylene glycol are taken, the copper acetylacetonate is dissolved in the ethylene glycol, and the zinc powder is added to obtain a mixed solution. Reacting the solution at 160 ℃ for 4h by using an oil bath method, annealing at 250 ℃ after the displacement reaction is finished, and etching with a dilute hydrochloric acid solution with the volume fraction of 5% for 30min to obtain porous copper micron hollow sphere powder with regular shape.
And (3) respectively cleaning 1 kg of hollow copper by adopting ultrapure water, ethanol and acetone for three times to remove impurities such as grease on the surface, and drying the cleaned product in vacuum for 6 hours to obtain the treated porous copper micron hollow sphere powder.
And adding 1 kg of treated porous copper micron hollow sphere powder into a glass container, adding 100 g of PAA serving as a binder and 0.5 kg of toluene serving as a solvent, and uniformly stirring to obtain porous copper micron hollow sphere slurry for later use, wherein the whole stirring temperature is 25 ℃.
And uniformly coating the mixed slurry on a copper foil by selecting a scraper with the specification of 100 micrometers, wherein the surface area of the copper foil is 1 square meter, and thus obtaining the coated pole piece. And drying the coated pole piece under the protection of argon (at 60 ℃) to obtain the porous copper micron hollow sphere current collector. And then, forming the porous copper micron hollow sphere current collector pole piece punching sheet according to the size of the battery pole piece.
The selected battery model is a 2032 type button battery, so the diameter of the pole piece is set to be 12 mm, and the obtained pole piece is a porous copper micron hollow sphere current collector. The porous copper micron hollow sphere current collector is assembled in a symmetrical battery to test the voltage hysteresis condition under large current, and the test value is 20mV, which proves that the porous copper micron hollow sphere current collector has good stability.
Example 11
One kilogram of commercial 5 micron zinc powder, 0.5 kilogram of copper acetylacetonate and 9.5 kilograms of ethylene glycol are taken, the copper acetylacetonate is dissolved in the ethylene glycol, and the zinc powder is added to obtain a mixed solution. Reacting the solution at 160 ℃ for 4h by using an oil bath method, annealing at 250 ℃ after the displacement reaction is finished, and etching with a dilute hydrochloric acid solution with the volume fraction of 5% for 30min to obtain porous copper micron hollow sphere powder with regular shape.
And (3) respectively cleaning 1 kg of porous copper micron hollow sphere powder with ultrapure water, ethanol and acetone for three times to remove impurities such as grease on the surface, and drying the cleaned product in vacuum for 6 hours to obtain the treated porous copper micron hollow sphere.
Adding 1 kg of processed micron hollow copper into a glass container, adding 100 g of PVDF as a binder and 0.5 kg of NMP as a solvent, and uniformly stirring to obtain porous copper micron hollow sphere slurry for later use, wherein the stirring temperature in the whole process is 25 ℃.
And dropping the mixed slurry on a copper foil, wherein the surface area of the copper foil is 1 square meter, and then spreading the copper foil on a substrate through high-speed rotation to form a uniform film, thereby obtaining the spin-coated pole piece. And drying the spin-coated pole piece under the protection of argon (at 60 ℃) to obtain the porous copper micron hollow sphere current collector. And then, forming the porous copper micron hollow sphere current collector pole piece punching sheet according to the size of the battery pole piece.
The selected battery model is a 2032 type button battery, so the diameter of the pole piece is set to be 12 mm, and the obtained pole piece is a porous copper micron hollow sphere current collector. The porous copper micron hollow sphere current collector is assembled in a symmetrical battery to test the voltage hysteresis condition under large current, and the test value is 20mV, which proves that the porous copper micron hollow sphere current collector has good stability.
Example 12
One kilogram of commercial 5 micron zinc powder, 0.5 kilogram of copper acetylacetonate and 9.5 kilograms of ethylene glycol are taken, the copper acetylacetonate is dissolved in the ethylene glycol, and the zinc powder is added to obtain a mixed solution. Reacting the solution at 160 ℃ for 4h by using an oil bath method, annealing at 250 ℃ after the displacement reaction is finished, and etching with a dilute hydrochloric acid solution with the volume fraction of 5% for 30min to obtain porous copper micron hollow sphere powder with regular shape.
And (3) respectively cleaning 1 kg of hollow copper by adopting ultrapure water, ethanol and acetone for three times to remove impurities such as grease on the surface, and drying the cleaned product in vacuum for 6 hours to obtain the treated porous copper micron hollow sphere powder.
And (3) adding 1 kg of treated porous copper micron hollow sphere powder into a glass container, adding 100 g of PVDF as a binder and 0.5 kg of NMP as a solvent, and uniformly stirring to obtain a porous copper micron hollow sphere slurry for later use, wherein the whole stirring temperature is 25 ℃.
And adding the mixed slurry onto a silk screen, and pressing and scraping the slurry on a silk screen mask by using a printing head to obtain the coated pole piece. And drying the coated pole piece under the protection of argon (at 60 ℃) to obtain the porous copper micron hollow sphere current collector. And then, forming the porous copper micron hollow sphere current collector pole piece punching sheet according to the size of the battery pole piece.
The selected battery model is a 2032 type button battery, so the diameter of the pole piece is set to be 12 mm, and the obtained pole piece is a porous copper micron hollow sphere current collector. The porous copper micron hollow sphere current collector is assembled in a symmetrical battery to test the voltage hysteresis condition under large current, and the test value is 17mV, which proves that the porous copper micron hollow sphere current collector has good stability.
Example 13
One kilogram of commercial 5 micron zinc powder, 0.5 kilogram of copper acetylacetonate and 9.5 kilograms of ethylene glycol are taken, the copper acetylacetonate is dissolved in the ethylene glycol, and the zinc powder is added to obtain a mixed solution. Reacting the solution at 160 ℃ for 4h by using an oil bath method, annealing at 250 ℃ after the displacement reaction is finished, and etching with a dilute hydrochloric acid solution with the volume fraction of 5% for 30min to obtain porous copper micron hollow sphere powder with regular shape.
And (3) respectively cleaning 1 kg of porous copper micron hollow sphere powder with ultrapure water, ethanol and acetone for three times to remove impurities such as grease on the surface, and drying the cleaned product in vacuum for 6 hours to obtain the treated porous copper micron hollow sphere current collector.
And adding 1 kg of treated porous copper micron hollow sphere powder into a glass container, adding 100 g of PVDF as a binder and 0.5 kg of NMP as a solvent, and uniformly stirring to obtain porous copper micron hollow sphere slurry for later use, wherein the whole stirring temperature is 25 ℃.
The mixed slurry is added into the 3D printer as ink, the pole piece structure can be accurately designed, and the controlled printed pole piece is obtained. And drying the printed pole piece under the protection of argon atmosphere (at 60 ℃) to obtain the porous copper micron hollow sphere current collector. And then, molding the porous copper micron hollow sphere current collector pole piece punching sheet according to the size of the battery pole piece.
The selected battery model is a 2032 type button battery, so the diameter of the pole piece is set to be 12 mm, and the obtained pole piece is a porous copper micron hollow sphere current collector. The porous copper micron hollow sphere current collector is assembled in a symmetrical battery to test the voltage hysteresis condition under large current, and the test value is 15mV, which proves that the porous copper micron hollow sphere current collector has good stability.
Example 14
One kilogram of commercial 5 micron zinc powder, 0.5 kilogram of copper acetylacetonate and 9.5 kilograms of ethylene glycol are taken, the copper acetylacetonate is dissolved in the ethylene glycol, and the zinc powder is added to obtain a mixed solution. Reacting the solution at 160 ℃ for 4h by using an oil bath method, annealing at 250 ℃ after the displacement reaction is finished, and etching with a dilute hydrochloric acid solution with the volume fraction of 5% for 30min to obtain porous copper micron hollow sphere powder with regular shape.
And (3) respectively cleaning 1 kg of porous copper micron hollow sphere powder with ultrapure water, ethanol and acetone for three times to remove impurities such as grease on the surface, and drying the cleaned product in vacuum for 6 hours to obtain the treated porous copper micron hollow sphere current collector.
And adding 1 kg of treated porous copper micron hollow sphere powder into a glass container, adding 100 g of PVDF as a binder and 0.5 kg of NMP as a solvent, and uniformly stirring to obtain porous copper micron hollow sphere powder slurry for later use, wherein the whole stirring temperature is 25 ℃.
And adding the mixed slurry into a spray gun, dispersing into uniform and fine droplets, and uniformly spraying on a copper foil, wherein the surface area of the copper foil is 1 square meter, so as to obtain the sprayed pole piece. And drying the sprayed pole piece under the protection of argon atmosphere (at 60 ℃) to obtain the porous copper micron hollow sphere current collector. And then, forming the porous copper micron hollow sphere current collector pole piece punching sheet according to the size of the battery pole piece.
The selected battery model is a 2032 type button battery, so the diameter of the pole piece is set to be 12 mm, and the obtained pole piece is a porous copper micron hollow sphere current collector. The porous copper micron hollow sphere current collector is assembled in a symmetrical battery to test the voltage hysteresis condition under large current, and the test value is 21mV, which proves that the porous copper micron hollow sphere current collector has good stability.
In conclusion, the negative plate of the three-dimensional porous hollow copper current collector obtained by the production method of the porous copper micron hollow sphere current collector can increase the specific surface area of the current collector, reduce the current density, reduce the internal contact resistance of copper and lithium, effectively inhibit the formation of dendritic crystal lithium, prevent the safety problems of short circuit and the like caused in the circulation process of the battery, greatly improve the safety, stability and service life of the battery, and the porous copper micron hollow sphere is light in weight, can contain more lithium, reduces the quality of inactive substances, improves the energy density of the battery, not only simplifies the production operation, but also reduces the pollution, energy consumption and cost.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. A production method of a porous copper micron hollow sphere current collector is characterized by comprising the following steps: the method mainly comprises the following steps:
step 1, taking a complex of zinc powder or zinc oxide powder and copper, and dissolving the complex of copper in a solvent to obtain a mixed solution;
step 2, placing the mixed solution in an environment of 160-180 ℃ for displacement reaction for 2-6 h;
step 3, annealing at 250-300 ℃ after the replacement reaction;
step 4, after etching in an etching solvent, carrying out vacuum drying to obtain porous copper micron hollow sphere powder with a regular shape;
step 5, grinding and mixing the porous copper micron hollow sphere powder obtained in the step 4 and a binder according to the mass ratio of 20:1, and dropwise adding a trace amount of organic solution to fully infiltrate the porous copper micron hollow sphere powder;
step 6, stirring for 2-4 hours at the speed of 600-800 r/min to obtain uniformly mixed slurry;
step 7, preparing the porous copper micron hollow sphere by liquid phase coating, high-temperature sintering, spin coating, screen printing and 3D printing, and combining the porous copper micron hollow sphere with the copper foil;
and 8, drying under the conditions of vacuum and 25-60 ℃ to obtain the porous copper micron hollow sphere current collector.
2. The method for producing the porous copper micro hollow sphere current collector as claimed in claim 1, wherein the method comprises the following steps: in step 1, the reactant zinc powder or zinc oxide powder is micron-grade reactant zinc powder or zinc oxide powder.
3. The method for producing the porous copper micro hollow sphere current collector as claimed in claim 1, wherein the method comprises the following steps: in step 1, the copper complex is copper acetylacetonate, copper tetraammine sulfate or copper tetraammine hydroxide.
4. The method for producing the porous copper micro hollow sphere current collector as claimed in claim 1, wherein the method comprises the following steps: in step 1, the solvent used to dissolve the copper complex is ethylene glycol or methanol.
5. The method for producing the porous copper micro-sphere current collector of claim 1, wherein: in step 3, the method of the displacement reaction is a solvothermal method or an oil bath heating method.
6. The method for producing the porous copper micro-sphere current collector of claim 1, wherein: in step 4, the etching solvent is 5 wt% diluted hydrochloric acid or diluted formic acid.
7. The method for producing the porous copper micro hollow sphere current collector as claimed in claim 1, wherein the method comprises the following steps: in step 4, the etching time is 0.5 to 6 hours, preferably 0.5 hour.
8. The method for producing the porous copper micro hollow sphere current collector as claimed in claim 1, wherein the method comprises the following steps: in step 5, the binder is at least one of polyvinylidene fluoride, polytetrafluoroethylene, acrylic resin emulsion and sodium carboxymethylcellulose; the solvent is a nonpolar or weak polar organic solvent, and the organic solvent is at least one of toluene, normal hexane, pentane, N-methyl pyrrolidone and styrene butadiene rubber.
9. The method for producing the porous copper micron hollow sphere current collector as claimed in claim 1, wherein the method comprises the following steps: in step 7, the bonding is by coating, spraying, spin coating or 3D printing.
10. The method for producing the porous copper micro hollow sphere current collector as claimed in claim 1, wherein the method comprises the following steps: the drying time in the step 8 is 0.5 to 24 hours, preferably 2 hours.
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