CN103779578A - Secondary-corrosion three-dimensional porous lithium battery current collector and preparation method thereof - Google Patents
Secondary-corrosion three-dimensional porous lithium battery current collector and preparation method thereof Download PDFInfo
- Publication number
- CN103779578A CN103779578A CN201410019709.6A CN201410019709A CN103779578A CN 103779578 A CN103779578 A CN 103779578A CN 201410019709 A CN201410019709 A CN 201410019709A CN 103779578 A CN103779578 A CN 103779578A
- Authority
- CN
- China
- Prior art keywords
- aluminium foil
- galvano
- cautery
- putting
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical fields of current collectors and electrochemical corrosion, particularly a secondary-corrosion three-dimensional porous lithium battery current collector and a preparation method thereof. The preparation method comprises the following steps: putting an aluminum foil into a phosphoric acid water solution to perform phosphoric acid corrosion treatment, putting the aluminum foil into a primary electric corrosion solution to perform primary power-on corrosion, putting the aluminum foil into a nitric acid water solution to perform nitric acid corrosion treatment, putting the aluminum foil into a secondary electric corrosion solution to perform secondary power-on corrosion, and finally, putting the aluminum foil into a chemical corrosion solution to perform chemical corrosion, thereby obtaining the secondary-corrosion three-dimensional porous lithium battery current collector. The current collector can increase the adsorption capacity of active substances, improve the common phenomena of peeling and swelling in the prior art, enhance the specific capacity, lower the contact resistance, increase the electric conductivity of the positive plate, enhance the charge and discharge capacity of the lithium battery, reduce the volume of the battery and prolong the service life of the battery.
Description
Technical field
the present invention relates to collector and electrochemical corrosion technical field, is that a kind of secondary corrodes three-dimensional porous lithium battery collector and preparation method thereof.
Background technology
lithium ion battery is as a kind of novel energy-storing power supply, there is the advantages such as energy is high, operating voltage is high, operating temperature range is wide, volume is little, quality is light, storage life is long, become new generation of green environment-friendly battery, and become rapidly the new lover in power supply market, replacing gradually NI-G, Ni-MH battery.Lithium-ion-power cell is in hybrid electric vehicle, electric automobile, electric bicycle, electronic manual facility market, and the aspect such as following solar LED street lamp energy storage device all has very large market application foreground; At detection system, the fuze system of modern military equipment as various weapons and device, also secondary power supply using lithium ion battery as high reliability all of aeroamphibious portable weapon, military communication and AEROSPACE APPLICATION aspect, therefore the research of the lithium-ion-power cell of good environmental adaptability, high specific energy, high security and miniaturization and is becoming at present study hotspot and future thrust both at home and abroad.Lithium ion battery is made up of positive pole, negative pole, barrier film, electrolyte and auxiliary material.Outer wrap at lithium ion battery has collector, traditional current collector material is generally selected ganoid aluminium foil, adopt the aluminium foil of 99.7% purity to be directly coated with and to be covered with active material, but the combination between ganoid aluminium foil and active material is comparatively lax, high to stock and adjunct quality and technological requirement, active material easily occurs in processing and charge and discharge process to come off or dry linting phenomenon, cycle charge discharge electrical efficiency and battery life are reduced, improve the contact resistance between components and parts, cause positive plate conductivity to decline, thereby affected the combination property of battery.Serious impact the combination property of lithium ion.In order to improve the contact resistance between components and parts, take to adopt mechanical mode in aluminium foil surface punching at aluminium foil surface at present, but still have the phenomenon that in charge and discharge process, easily generation active material comes off or dry linting is serious; Also having a kind of way is after aluminium foil surface applies one deck activated carbon, to be re-used as collector to use, but the method has increased technological process and processing cost; Also can adopt inexpensive thin Graphene as collector, but this technique not yet realizes industrialization, technical threshold is relatively high, and raw material and technical staff are required also to have higher requirement.
Summary of the invention
the invention provides a kind of secondary and corrode three-dimensional porous lithium battery collector and preparation method thereof, overcome the deficiency of above-mentioned prior art, it can effectively solve takes off powder phenomenon in prior art and causes the problem that contact resistance is high.
one of technical scheme of the present invention realizes by following measures: a kind of secondary corrodes three-dimensional porous lithium battery collector, obtain as follows: the first step, by putting into 0.1g to 1g aluminium foil in every liter of phosphate aqueous solution, it is 0.1% to 20% phosphate aqueous solution that aluminium foil is put into mass concentration, is under 20 ℃ to 80 ℃ conditions, to carry out phosphoric acid corrosion to process 30s to 10min in temperature; Second step, by putting into 0.1g to 5g aluminium foil in every liter of one-level galvano-cautery liquid, will put into one-level galvano-cautery liquid through phosphoric acid corrosion aluminium foil after treatment, with 1Hz industrial-frequency alternating current be 1A/cm in current density
2
to 20 A/cm
2
, temperature is under 25 ℃ to 60 ℃ conditions, to carry out one-level to add galvano-cautery 10s to 5min; The 3rd step, by putting into 0.1g to 1g aluminium foil in every liter of aqueous solution of nitric acid, aluminium foil after one-level adds galvano-cautery is put into the aqueous solution of nitric acid that concentration is 0.01mol/L to 1mol/L, is to carry out nitric acid corrosion treatment 30s to 10min under 25 ℃ to 60 ℃ conditions in temperature; The 4th step, by putting into 0.1g to 5g aluminium foil in every liter of secondary galvano-cautery liquid, puts into secondary galvano-cautery liquid by the aluminium foil after pernitric acid corrosion treatment, with 50Hz industrial-frequency alternating current be 0.133A/cm in current density
2
to 10 A/cm
2
, temperature is under 10 ℃ to 80 ℃ conditions, to carry out secondary to add galvano-cautery 10s to 5min; The 5th step, by putting into 0.1g to 5g aluminium foil in every liter of chemical corrosion liquid, aluminium foil after secondary adds galvano-cautery is put into chemical corrosion liquid, is under 25 ℃ to 45 ℃ conditions, to carry out chemical corrosion 30s to 10min to obtain secondary and corrode three-dimensional porous lithium battery collector in temperature.
two of technical scheme of the present invention realizes by following measures: a kind of secondary corrodes the preparation method of three-dimensional porous lithium battery collector, carry out in the steps below: the first step, by putting into 0.1g to 1g aluminium foil in every liter of phosphate aqueous solution, it is 0.1% to 20% phosphate aqueous solution that aluminium foil is put into mass concentration, is under 20 ℃ to 80 ℃ conditions, to carry out phosphoric acid corrosion to process 30s to 10min in temperature; Second step, by putting into 0.1g to 5g aluminium foil in every liter of one-level galvano-cautery liquid, will put into one-level galvano-cautery liquid through phosphoric acid corrosion aluminium foil after treatment, with 1Hz industrial-frequency alternating current be 1A/cm in current density
2
to 20 A/cm
2
, temperature is under 25 ℃ to 60 ℃ conditions, to carry out one-level to add galvano-cautery 10s to 5min; The 3rd step, by putting into 0.1g to 1g aluminium foil in every liter of aqueous solution of nitric acid, aluminium foil after one-level adds galvano-cautery is put into the aqueous solution of nitric acid that concentration is 0.01mol/L to 1mol/L, is to carry out nitric acid corrosion treatment 30s to 10min under 25 ℃ to 60 ℃ conditions in temperature; The 4th step, by putting into 0.1g to 5g aluminium foil in every liter of secondary galvano-cautery liquid, puts into secondary galvano-cautery liquid by the aluminium foil after pernitric acid corrosion treatment, with 50Hz industrial-frequency alternating current be 0.133A/cm in current density
2
to 10 A/cm
2
, temperature is under 10 ℃ to 80 ℃ conditions, to carry out secondary to add galvano-cautery 10s to 5min; The 5th step, by putting into 0.1g to 5g aluminium foil in every liter of chemical corrosion liquid, aluminium foil after secondary adds galvano-cautery is put into chemical corrosion liquid, is under 25 ℃ to 45 ℃ conditions, to carry out chemical corrosion 30s to 10min to obtain secondary and corrode three-dimensional porous lithium battery collector in temperature.
the further optimization and/or improvements to foregoing invention technical scheme below:
in the above-mentioned first step, by putting into 0.45g aluminium foil in every liter of phosphate aqueous solution, it is 0.1% to 20% phosphate aqueous solution that aluminium foil is put into mass concentration; In second step, by putting into 1.5g aluminium foil in every liter of one-level galvano-cautery liquid, will put into one-level galvano-cautery liquid through phosphoric acid corrosion aluminium foil after treatment; In the 3rd step, by putting into 0.45g aluminium foil in every liter of aqueous solution of nitric acid, the aluminium foil after one-level adds galvano-cautery is put into the aqueous solution of nitric acid that concentration is 0.01mol/L to 1mol/L; In the 4th step, by putting into 1.5g aluminium foil in every liter of secondary galvano-cautery liquid, the aluminium foil after pernitric acid corrosion treatment is put into secondary galvano-cautery liquid; In the 5th step, by putting into 0.45g aluminium foil in every liter of chemical corrosion liquid, the aluminium foil after secondary adds galvano-cautery is put into chemical corrosion liquid.
above-mentioned secondary galvano-cautery liquid is to be that 1mol/L to 8mol/L, sulfuric acid concentration are that 0.001mol/L to 0.9mol/L, additive A concentration are that 0.01mol/L to 0.1mol/L, additive B concentration are the solution that 0.001mol/L to 0.1mol/L, aluminium ion concentration are 0.1mol/L to 2mol/L by the concentration of hydrochloric acid that is mixed with soluble in water to hydrochloric acid, sulfuric acid, additive A, additive B and aluminum contained compound.
above-mentioned additive A is one or both mixtures that form by any ratio in citric acid, oxalic acid and adipic acid; Or/and additive B is one or both mixtures that form by any ratio in thiocarbamide, acrylic acid and ethylene glycol.
above-mentioned one-level galvano-cautery liquid is to be that 1mol/L to 8mol/L, sulfuric acid concentration are the solution that 0.001mol/L to 0.9mol/L, aluminium ion concentration are 0.5mol/L to 1mol/L by the concentration of hydrochloric acid that is mixed with soluble in water to hydrochloric acid, sulfuric acid and aluminum contained compound; Or/and chemical corrosion liquid is to be that 0.1mol/L to 5mol/L, aluminium composition are the solution of 0.1 mol/L to 2mol/L by nitric acid and the aluminum contained compound concentration of nitric acid that is mixed with soluble in water.
the present invention can increase active material adsorption capacity, improves the dry linting often running in prior art, swelling shedding phenomenon, increases specific capacity, reduce contact resistance, increase positive plate plate conductivity, improve charging and discharging lithium battery capacity, can reduce battery volume, extending battery life simultaneously.
Accompanying drawing explanation
accompanying drawing 1 is 1000 times of scanning electron microscope (SEM) photographs of the present invention.
accompanying drawing 2 is 5000 times of scanning electron microscope (SEM) photographs of the present invention.
Embodiment
the present invention is not subject to the restriction of following embodiment, can determine concrete execution mode according to technical scheme of the present invention and actual conditions.
below in conjunction with embodiment and accompanying drawing, the invention will be further described:
embodiment 1, this secondary corrodes three-dimensional porous lithium battery collector and obtains by following preparation method: the first step, by putting into 0.1g to 1g aluminium foil in every liter of phosphate aqueous solution, it is 0.1% to 20% phosphate aqueous solution that aluminium foil is put into mass concentration, is under 20 ℃ to 80 ℃ conditions, to carry out phosphoric acid corrosion to process 30s to 10min in temperature; Second step, by putting into 0.1g to 5g aluminium foil in every liter of one-level galvano-cautery liquid, will put into one-level galvano-cautery liquid through phosphoric acid corrosion aluminium foil after treatment, with 1Hz industrial-frequency alternating current be 1A/cm in current density
2
to 20 A/cm
2
, temperature is under 25 ℃ to 60 ℃ conditions, to carry out one-level to add galvano-cautery 10s to 5min; The 3rd step, by putting into 0.1g to 1g aluminium foil in every liter of aqueous solution of nitric acid, aluminium foil after one-level adds galvano-cautery is put into the aqueous solution of nitric acid that concentration is 0.01mol/L to 1mol/L, is to carry out nitric acid corrosion treatment 30s to 10min under 25 ℃ to 60 ℃ conditions in temperature; The 4th step, by putting into 0.1g to 5g aluminium foil in every liter of secondary galvano-cautery liquid, puts into secondary galvano-cautery liquid by the aluminium foil after pernitric acid corrosion treatment, with 50Hz industrial-frequency alternating current be 0.133A/cm in current density
2
to 10 A/cm
2
, temperature is under 10 ℃ to 80 ℃ conditions, to carry out secondary to add galvano-cautery 10s to 5min; The 5th step, by putting into 0.1g to 5g aluminium foil in every liter of chemical corrosion liquid, aluminium foil after secondary adds galvano-cautery is put into chemical corrosion liquid, is under 25 ℃ to 45 ℃ conditions, to carry out chemical corrosion 30s to 10min to obtain secondary and corrode three-dimensional porous lithium battery collector in temperature.Phosphoric acid corrosion processing can wash away the blemish such as air oxidation film, greasy dirt being attached to above aluminium foil; Adopt suitable pre-treating technology to remove oxide-film, the greasy dirt etc. of aluminium foil surface, carry out one-level with 1Hz low frequency ac and add galvano-cautery at aluminium foil surface formation one deck wedge shape square hole, approximately 1 micron of hole depth, approximately 2 microns, aperture, then in aqueous solution of nitric acid, remove the copper of aluminium foil surface enrichment; Then under 50Hz industrial-frequency alternating current, carry out secondary and add galvano-cautery, obtain tiny worm-eaten hole, the object of wedged hole is the static capacity that increases aluminium foil, for the charge/discharge capacity of lithium battery is contributed; Tiny worm-eaten hole is in order to increase aluminium foil surface roughness, increases contact area, improves the absorption affinity of active material, reduces the contact resistance between aluminium foil and active material; After assembling with lithium battery, compared with traditional aluminium foil collector, the charging and discharging capabilities of lithium battery has improved more than 5%.
embodiment 2, this secondary corrodes three-dimensional porous lithium battery collector and obtains by following preparation method: the first step, by putting into 0.1g or 1g aluminium foil in every liter of phosphate aqueous solution, it is 0.1% or 20% phosphate aqueous solution that aluminium foil is put into mass concentration, carries out phosphoric acid corrosion and process 30s or 10min under temperature is 20 ℃ or 80 ℃ of conditions; Second step, by putting into 0.1g or 5g aluminium foil in every liter of one-level galvano-cautery liquid, will put into one-level galvano-cautery liquid through phosphoric acid corrosion aluminium foil after treatment, with 1Hz industrial-frequency alternating current be 1A/cm in current density
2
or 20 A/cm
2
, temperature is under 25 ℃ or 60 ℃ of conditions, to carry out one-level to add galvano-cautery 10s or 5min; The 3rd step, by putting into 0.1g or 1g aluminium foil in every liter of aqueous solution of nitric acid, aluminium foil after one-level adds galvano-cautery is put into the aqueous solution of nitric acid that concentration is 0.01mol/L or 1mol/L, under temperature is 25 ℃ or 60 ℃ of conditions, carry out nitric acid corrosion treatment 30s or 10min; The 4th step, by putting into 0.1g or 5g aluminium foil in every liter of secondary galvano-cautery liquid, puts into secondary galvano-cautery liquid by the aluminium foil after pernitric acid corrosion treatment, with 50Hz industrial-frequency alternating current be 0.133A/cm in current density
2
or 10 A/cm
2
, temperature is under 10 ℃ or 80 ℃ of conditions, to carry out secondary to add galvano-cautery 10s or 5min; The 5th step, by putting into 0.1g or 5g aluminium foil in every liter of chemical corrosion liquid, aluminium foil after secondary adds galvano-cautery is put into chemical corrosion liquid, under temperature is 25 ℃ or 45 ℃ of conditions, carry out chemical corrosion 30s or 10min and obtain secondary and corrode three-dimensional porous lithium battery collector.
embodiment 3, in the first step, by putting into 0.45g aluminium foil in every liter of phosphate aqueous solution, it is 0.1% to 20% phosphate aqueous solution that aluminium foil is put into mass concentration; In second step, by putting into 1.5g aluminium foil in every liter of one-level galvano-cautery liquid, will put into one-level galvano-cautery liquid through phosphoric acid corrosion aluminium foil after treatment; In the 3rd step, by putting into 0.45g aluminium foil in every liter of aqueous solution of nitric acid, the aluminium foil after one-level adds galvano-cautery is put into the aqueous solution of nitric acid that concentration is 0.01mol/L to 1mol/L; In the 4th step, by putting into 1.5g aluminium foil in every liter of secondary galvano-cautery liquid, the aluminium foil after pernitric acid corrosion treatment is put into secondary galvano-cautery liquid; In the 5th step, by putting into 0.45g aluminium foil in every liter of chemical corrosion liquid, the aluminium foil after secondary adds galvano-cautery is put into chemical corrosion liquid.
embodiment 4, secondary galvano-cautery liquid is to be that 1mol/L to 8mol/L, sulfuric acid concentration are that 0.001mol/L to 0.9mol/L, additive A concentration are that 0.01mol/L to 0.1mol/L, additive B concentration are the solution that 0.001mol/L to 0.1mol/L, aluminium ion concentration are 0.1mol/L to 2mol/L by the concentration of hydrochloric acid that is mixed with soluble in water to hydrochloric acid, sulfuric acid, additive A, additive B and aluminum contained compound.
embodiment 5, additive A is one or both mixtures that form by any ratio in citric acid, oxalic acid and adipic acid; Or/and additive B is one or both mixtures that form by any ratio in thiocarbamide, acrylic acid and ethylene glycol.
embodiment 6, one-level galvano-cautery liquid is to be that 1mol/L to 8mol/L, sulfuric acid concentration are the solution that 0.001mol/L to 0.9mol/L, aluminium ion concentration are 0.5mol/L to 1mol/L by the concentration of hydrochloric acid that is mixed with soluble in water to hydrochloric acid, sulfuric acid and aluminum contained compound; Or/and chemical corrosion liquid is to be that 0.1mol/L to 5mol/L, aluminium composition are the solution of 0.1 mol/L to 2mol/L by nitric acid and the aluminum contained compound concentration of nitric acid that is mixed with soluble in water.
the present invention first removes the blemish such as air oxidation film, greasy dirt that is attached to aluminium foil surface; Then carry out one-level with 1Hz low frequency ac and add galvano-cautery at aluminium foil surface formation one deck wedge shape square hole, approximately 1 micron of hole depth, approximately 2 microns, aperture, then in aqueous solution of nitric acid, remove the copper of aluminium foil surface enrichment; Then under 50Hz industrial-frequency alternating current, carry out secondary and add galvano-cautery, obtain tiny worm-eaten hole, make it the surface uniform three-dimensional hole that distributes, wedge shape square hole and tiny worm-eaten pore structure can be found out by Fig. 1 and Fig. 2.The object of wedged hole is the static capacity that increases aluminium foil, for the charge/discharge capacity of lithium battery is contributed; Tiny worm-eaten hole is in order to increase aluminium foil surface roughness, increase contact area, improve the absorption affinity of active material, reduce the contact resistance between aluminium foil and active material, aluminium foil surface does not have the existing tiny corrosion product of conventional electrodes paper tinsel product simultaneously, can prevent the shedding of later stage active material, also contribute for reducing contact resistance; After assembling with lithium battery, compared with traditional aluminium foil collector, the charging and discharging capabilities of lithium battery has improved more than 5%; Can increase active material adsorption capacity by the present invention, improve dry linting, swelling shedding phenomenon that prior art often runs into, increase specific capacity, reduce contact resistance, increase positive plate plate conductivity, improve charging and discharging lithium battery capacity more than 5%, can reduce battery volume, extending battery life simultaneously; The secondary obtaining according to the inventive method corrodes three-dimensional porous lithium battery collector can be applied to lithium ion battery and current collector of super capacitor field, is applicable to the active material that particle diameter is 100nm to 1 μ m.
Claims (10)
1. a secondary corrodes three-dimensional porous lithium battery collector, it is characterized in that obtaining as follows: the first step, by putting into 0.1g to 1g aluminium foil in every liter of phosphate aqueous solution, it is 0.1% to 20% phosphate aqueous solution that aluminium foil is put into mass concentration, is under 20 ℃ to 80 ℃ conditions, to carry out phosphoric acid corrosion to process 30s to 10min in temperature; Second step, by putting into 0.1g to 5g aluminium foil in every liter of one-level galvano-cautery liquid, will put into one-level galvano-cautery liquid through phosphoric acid corrosion aluminium foil after treatment, with 1Hz industrial-frequency alternating current be 1A/cm in current density
2to 20 A/cm
2, temperature is under 25 ℃ to 60 ℃ conditions, to carry out one-level to add galvano-cautery 10s to 5min; The 3rd step, by putting into 0.1g to 1g aluminium foil in every liter of aqueous solution of nitric acid, aluminium foil after one-level adds galvano-cautery is put into the aqueous solution of nitric acid that concentration is 0.01mol/L to 1mol/L, is to carry out nitric acid corrosion treatment 30s to 10min under 25 ℃ to 60 ℃ conditions in temperature; The 4th step, by putting into 0.1g to 5g aluminium foil in every liter of secondary galvano-cautery liquid, puts into secondary galvano-cautery liquid by the aluminium foil after pernitric acid corrosion treatment, with 50Hz industrial-frequency alternating current be 0.133A/cm in current density
2to 10 A/cm
2, temperature is under 10 ℃ to 80 ℃ conditions, to carry out secondary to add galvano-cautery 10s to 5min; The 5th step, by putting into 0.1g to 5g aluminium foil in every liter of chemical corrosion liquid, aluminium foil after secondary adds galvano-cautery is put into chemical corrosion liquid, is under 25 ℃ to 45 ℃ conditions, to carry out chemical corrosion 30s to 10min to obtain secondary and corrode three-dimensional porous lithium battery collector in temperature.
2. secondary according to claim 1 corrodes three-dimensional porous lithium battery collector, it is characterized in that in the first step by putting into 0.45g aluminium foil in every liter of phosphate aqueous solution, and it is 0.1% to 20% phosphate aqueous solution that aluminium foil is put into mass concentration; In second step, by putting into 1.5g aluminium foil in every liter of one-level galvano-cautery liquid, will put into one-level galvano-cautery liquid through phosphoric acid corrosion aluminium foil after treatment; In the 3rd step, by putting into 0.45g aluminium foil in every liter of aqueous solution of nitric acid, the aluminium foil after one-level adds galvano-cautery is put into the aqueous solution of nitric acid that concentration is 0.01mol/L to 1mol/L; In the 4th step, by putting into 1.5g aluminium foil in every liter of secondary galvano-cautery liquid, the aluminium foil after pernitric acid corrosion treatment is put into secondary galvano-cautery liquid; In the 5th step, by putting into 0.45g aluminium foil in every liter of chemical corrosion liquid, the aluminium foil after secondary adds galvano-cautery is put into chemical corrosion liquid.
3. secondary according to claim 1 and 2 corrodes three-dimensional porous lithium battery collector, it is characterized in that secondary galvano-cautery liquid is is that 1mol/L to 8mol/L, sulfuric acid concentration are that 0.001mol/L to 0.9mol/L, additive A concentration are that 0.01mol/L to 0.1mol/L, additive B concentration are the solution that 0.001mol/L to 0.1mol/L, aluminium ion concentration are 0.1mol/L to 2mol/L by the concentration of hydrochloric acid that is mixed with soluble in water to hydrochloric acid, sulfuric acid, additive A, additive B and aluminum contained compound.
4. secondary according to claim 3 corrodes three-dimensional porous lithium battery collector, it is characterized in that additive A is one or both mixtures that form by any ratio in citric acid, oxalic acid and adipic acid; Or/and additive B is one or both mixtures that form by any ratio in thiocarbamide, acrylic acid and ethylene glycol.
5. corrode three-dimensional porous lithium battery collector according to the secondary described in claim 1 or 2 or 3 or 4, it is characterized in that one-level galvano-cautery liquid is is that 1mol/L to 8mol/L, sulfuric acid concentration are the solution that 0.001mol/L to 0.9mol/L, aluminium ion concentration are 0.5mol/L to 1mol/L by the concentration of hydrochloric acid that is mixed with soluble in water to hydrochloric acid, sulfuric acid and aluminum contained compound; Or/and chemical corrosion liquid is to be that 0.1mol/L to 5mol/L, aluminium composition are the solution of 0.1 mol/L to 2mol/L by nitric acid and the aluminum contained compound concentration of nitric acid that is mixed with soluble in water.
6. the preparation method that secondary corrodes three-dimensional porous lithium battery collector, it is characterized in that carrying out in the steps below: the first step, by putting into 0.1g to 1g aluminium foil in every liter of phosphate aqueous solution, it is 0.1% to 20% phosphate aqueous solution that aluminium foil is put into mass concentration, is under 20 ℃ to 80 ℃ conditions, to carry out phosphoric acid corrosion to process 30s to 10min in temperature; Second step, by putting into 0.1g to 5g aluminium foil in every liter of one-level galvano-cautery liquid, will put into one-level galvano-cautery liquid through phosphoric acid corrosion aluminium foil after treatment, with 1Hz industrial-frequency alternating current be 1A/cm in current density
2to 20 A/cm
2, temperature is under 25 ℃ to 60 ℃ conditions, to carry out one-level to add galvano-cautery 10s to 5min; The 3rd step, by putting into 0.1g to 1g aluminium foil in every liter of aqueous solution of nitric acid, aluminium foil after one-level adds galvano-cautery is put into the aqueous solution of nitric acid that concentration is 0.01mol/L to 1mol/L, is to carry out nitric acid corrosion treatment 30s to 10min under 25 ℃ to 60 ℃ conditions in temperature; The 4th step, by putting into 0.1g to 5g aluminium foil in every liter of secondary galvano-cautery liquid, puts into secondary galvano-cautery liquid by the aluminium foil after pernitric acid corrosion treatment, with 50Hz industrial-frequency alternating current be 0.133A/cm in current density
2to 10 A/cm
2, temperature is under 10 ℃ to 80 ℃ conditions, to carry out secondary to add galvano-cautery 10s to 5min; The 5th step, by putting into 0.1g to 5g aluminium foil in every liter of chemical corrosion liquid, aluminium foil after secondary adds galvano-cautery is put into chemical corrosion liquid, is under 25 ℃ to 45 ℃ conditions, to carry out chemical corrosion 30s to 10min to obtain secondary and corrode three-dimensional porous lithium battery collector in temperature.
7. secondary according to claim 6 corrodes the preparation method of three-dimensional porous lithium battery collector, it is characterized in that in the first step by putting into 0.45g aluminium foil in every liter of phosphate aqueous solution, and it is 0.1% to 20% phosphate aqueous solution that aluminium foil is put into mass concentration; In second step, by putting into 1.5g aluminium foil in every liter of one-level galvano-cautery liquid, will put into one-level galvano-cautery liquid through phosphoric acid corrosion aluminium foil after treatment; In the 3rd step, by putting into 0.45g aluminium foil in every liter of aqueous solution of nitric acid, the aluminium foil after one-level adds galvano-cautery is put into the aqueous solution of nitric acid that concentration is 0.01mol/L to 1mol/L; In the 4th step, by putting into 1.5g aluminium foil in every liter of secondary galvano-cautery liquid, the aluminium foil after pernitric acid corrosion treatment is put into secondary galvano-cautery liquid; In the 5th step, by putting into 0.45g aluminium foil in every liter of chemical corrosion liquid, the aluminium foil after secondary adds galvano-cautery is put into chemical corrosion liquid.
8. corrode the preparation method of three-dimensional porous lithium battery collector according to the secondary described in claim 6 or 7, it is characterized in that secondary galvano-cautery liquid is is that 1mol/L to 8mol/L, sulfuric acid concentration are that 0.001mol/L to 0.9mol/L, additive A concentration are that 0.01mol/L to 0.1mol/L, additive B concentration are the solution that 0.001mol/L to 0.1mol/L, aluminium ion concentration are 0.1mol/L to 2mol/L by the concentration of hydrochloric acid that is mixed with soluble in water to hydrochloric acid, sulfuric acid, additive A, additive B and aluminum contained compound.
9. secondary according to claim 8 corrodes the preparation method of three-dimensional porous lithium battery collector, it is characterized in that additive A is one or both mixtures that form by any ratio in citric acid, oxalic acid and adipic acid; Or/and additive B is one or both mixtures that form by any ratio in thiocarbamide, acrylic acid and ethylene glycol.
10. the preparation method of corroding three-dimensional porous lithium battery collector according to the secondary described in claim 6 or 7 or 8 or 9, is characterized in that one-level galvano-cautery liquid is is that 1mol/L to 8mol/L, sulfuric acid concentration are the solution that 0.001mol/L to 0.9mol/L, aluminium ion concentration are 0.5mol/L to 1mol/L by the concentration of hydrochloric acid that is mixed with soluble in water to hydrochloric acid, sulfuric acid and aluminum contained compound; Or/and chemical corrosion liquid is to be that 0.1mol/L to 5mol/L, aluminium composition are the solution of 0.1 mol/L to 2mol/L by nitric acid and the aluminum contained compound concentration of nitric acid that is mixed with soluble in water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410019709.6A CN103779578B (en) | 2014-01-16 | 2014-01-16 | Two grades corrode three-dimensional porous lithium battery collector and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410019709.6A CN103779578B (en) | 2014-01-16 | 2014-01-16 | Two grades corrode three-dimensional porous lithium battery collector and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103779578A true CN103779578A (en) | 2014-05-07 |
| CN103779578B CN103779578B (en) | 2016-06-29 |
Family
ID=50571586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410019709.6A Active CN103779578B (en) | 2014-01-16 | 2014-01-16 | Two grades corrode three-dimensional porous lithium battery collector and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103779578B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107177879A (en) * | 2017-03-21 | 2017-09-19 | 广东宇彤创业投资有限公司 | A kind of preparation method of perforated foil |
| CN108417843A (en) * | 2018-02-23 | 2018-08-17 | 天津大学 | A kind of porous aluminum collector inhibiting sodium dendrite |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4420367A (en) * | 1981-05-07 | 1983-12-13 | Siemens Aktiengesellschaft | Method for etching a recrystallized aluminum foil for electrolytic capacitors |
| CN1542881A (en) * | 2003-05-15 | 2004-11-03 | 扬州宏远电子有限公司 | Etching technique of hard foil |
| CN1585060A (en) * | 2004-06-14 | 2005-02-23 | 扬州宏远电子有限公司 | Process for etching 63 WV-100WV anode foils with high-specific capacity |
| CN1920114A (en) * | 2006-08-02 | 2007-02-28 | 扬州宏远电子有限公司 | Corrosion method of anode foil for low-voltage aluminum electrolytic capacitor |
-
2014
- 2014-01-16 CN CN201410019709.6A patent/CN103779578B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4420367A (en) * | 1981-05-07 | 1983-12-13 | Siemens Aktiengesellschaft | Method for etching a recrystallized aluminum foil for electrolytic capacitors |
| CN1542881A (en) * | 2003-05-15 | 2004-11-03 | 扬州宏远电子有限公司 | Etching technique of hard foil |
| CN1585060A (en) * | 2004-06-14 | 2005-02-23 | 扬州宏远电子有限公司 | Process for etching 63 WV-100WV anode foils with high-specific capacity |
| CN1920114A (en) * | 2006-08-02 | 2007-02-28 | 扬州宏远电子有限公司 | Corrosion method of anode foil for low-voltage aluminum electrolytic capacitor |
Non-Patent Citations (1)
| Title |
|---|
| 王玫 等: "影响高压阳极铝箔隧道孔极限长度的因素", 《电子元件与试剂》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107177879A (en) * | 2017-03-21 | 2017-09-19 | 广东宇彤创业投资有限公司 | A kind of preparation method of perforated foil |
| CN108417843A (en) * | 2018-02-23 | 2018-08-17 | 天津大学 | A kind of porous aluminum collector inhibiting sodium dendrite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103779578B (en) | 2016-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11728489B2 (en) | Three-dimensional current collector for metal secondary battery anode, its preparation and application | |
| CN105140477A (en) | Silicon carbon composite material and preparation method thereof | |
| CN103346301A (en) | Preparation method and application of three-dimensional-structure graphene-base metal oxide composite material | |
| CN103779577A (en) | Three-dimensional porous lithium battery current collector and preparation method thereof | |
| CN202308155U (en) | High-security capacitor battery | |
| CN104425134A (en) | High-porosity and high-conductivity porous electrode, batch manufacturing process of porous electrode and super pseudo-capacitor using porous electrode | |
| CN103035920A (en) | Lithium-ion battery and preparation method thereof | |
| CN107403908A (en) | A kind of method for suppressing lithium titanate battery flatulence | |
| CN102881951A (en) | Capacitor battery with high safety | |
| CN105293467A (en) | Phenolic resin/coal tar pitch composite-base modified hard carbon negative electrode material and preparation method and application thereof | |
| CN102842703A (en) | Chemical power supply | |
| CN104021945B (en) | A kind of high power density and high-energy density super capacitor and preparation method thereof | |
| JP2010109080A (en) | Method for manufacturing electrode for storage element, electrode for storage element, and nonaqueous lithium type electricity storage element | |
| CN111146007A (en) | Zinc ion hybrid supercapacitor and preparation method thereof | |
| CN103779578B (en) | Two grades corrode three-dimensional porous lithium battery collector and preparation method thereof | |
| CN101894686A (en) | Super capacitor battery | |
| CN104752687A (en) | Production method of polymer lithium ion battery positive and negative current collectors | |
| CN202018886U (en) | Composite film medium filter capacitor | |
| US10121605B2 (en) | Wide operating temperature range electrolytes for lithium-ion capacitors achieving high performance | |
| CN105470467B (en) | A kind of preparation method of high security alminium electrolytic condenser type cobalt acid lithium lithium ion battery | |
| CN207183416U (en) | A kind of three-dimensional lithium ion battery | |
| CN102544576A (en) | Lithium ion battery | |
| CN101763948A (en) | Acid super-capacitor | |
| CN105406132A (en) | High-safety aluminium electrolytic capacitor type nickel-cobalt-manganese ternary material lithium ion battery | |
| CN105895889B (en) | A kind of preparation method of lithium ion battery plus plate current-collecting body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |