CN109036852A - A kind of porous aluminum electric pole foil of novel three-dimensional and preparation method thereof - Google Patents
A kind of porous aluminum electric pole foil of novel three-dimensional and preparation method thereof Download PDFInfo
- Publication number
- CN109036852A CN109036852A CN201810913489.XA CN201810913489A CN109036852A CN 109036852 A CN109036852 A CN 109036852A CN 201810913489 A CN201810913489 A CN 201810913489A CN 109036852 A CN109036852 A CN 109036852A
- Authority
- CN
- China
- Prior art keywords
- foil
- powder
- porous
- electric pole
- aluminium
- 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
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
-
- 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
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/002—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature
- B22F7/004—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature comprising at least one non-porous part
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/055—Etched foil electrodes
Abstract
The present invention provides a kind of porous aluminum electric pole foils of novel three-dimensional, the electrode foil includes Al foil substrate and the compound porous aluminium film formed by mixed powder on Al foil substrate two sides, the overall thickness of electrode foil is 80 μm -200 μm, voltage is 300-600V, bending times are returned for 50-340, and specific volume is 0.70-2.55 μ F/cm2.Simultaneously the present invention also provides a kind of method for preparing the porous aluminum electric pole foil of above-mentioned novel three-dimensional, this method will contain aluminium powder, aluminum fiber and high dielectric oxide powder first and be mixed into mixed powder；Mixed powder is dispersed in Al foil substrate two sides again, and carries out compacting and forms closely packed porous foil；Then porous foil is subjected to thermalization processing, and controlling the porosity by extrusion process is 35%-45%, with a thickness of 80 μm -200 μm；Finally by thermalization, treated that porous aluminum electric pole foil carries out formation energy-endowing processing.Three-dimensional porous aluminum electric pole foil provided by the invention has the performances such as Fabrication of High Specific Capacitance and high intensity, and the compound porous aluminium film on Al foil substrate has the characteristics that binding force is good in process of production without cracking, without falling off.
Description
Technical field
The present invention relates to a kind of porous aluminum electric pole foils of the novel three-dimensional for aluminium electrolutic capacitor, more particularly, to middle high
The anode electrode foil and its manufacturing method of pressure and ultra-high voltage aluminum electrolytic capacitor.
Background technique
Electrode foil is the key raw material of aluminium electrolutic capacitor, and aluminium electrolutic capacitor is various household electrical appliance, computer, leads to
Interrogate one of three big components that must be used such as equipment, automation equipment.The quality of electrode foil is related to the use longevity of capacitor
Life, directly affects the service life of complete electronic set.As electronics industry develops rapidly, the use of aluminium electroloysis container is more extensive,
Miniaturization, service life length, highly reliable requirement are increasingly urgent to, and electrode foil processing technology also becomes the core of aluminium electrolutic capacitor manufacture
One of heart technology will obtain small form factor requirements, it is necessary to reach Fabrication of High Specific Capacitance, especially high-intensitive requirement.Traditional electrode foil passes through
Implement electrochemical etch process and form tunnel defect, is capable of increasing surface area, but Tunnel-hole diameter length is difficult to equal control, mesh
The problem of preceding KDK and JCC control is ideal, but Fabrication of High Specific Capacitance etched foil, brings intensity is poor, it is difficult to which cutting winding is not suitable for
Capacitor miniaturization.In the formation energy-endowing stage, with the raising of voltage, the thickness of oxidation film increases, the aluminum substrate of internal residual
It reduces, intensity declines to a great extent, and Fabrication of High Specific Capacitance electrode foil is difficult to be suitable for the aluminium electrolutic capacitor of high pressure and super-pressure.And tradition
Etch process need to use the environmental pollutions raw material such as a large amount of hydrochloric acid, sulfuric acid and nitric acid, very big pressure is brought to environmental protection treatment
Power.
In recent years, it proposes through sputtering, vapor deposition, the sintered body of the porous aluminium powder made of modes such as sintering replaces implementing losing
Quarter processing makes the method for the aluminium anodes electrode foil after surface area increase, such as Chinese patent CN 102714098B, CN
102804302A, CN 103688327A, CN 104409215A, have in CN 104919552A and to mention with aluminium and aluminium alloy
Powder is configured to slurry coating on metal base, is then sintered, forms porous sintered layer, to increase paillon specific surface area
Effect.Confirm the electrode foil for aluminum electrolytic capacitors obtained by the sintered body of porous aluminium powder, surface area, which is more than or equal to, to be passed through
The pit area that etching process is formed.But it sputters, evaporation thickness is difficult to improve, and is suitable for cathode or low-voltage foil, because of mesohigh and is surpassed
High pressure needs fewer defects, to reduce leakage current, improves the service life of capacitor, also has using high dielectric material such as TiO2
Etc. high dielectric constants substance, for high pressure and super-pressure, there are binding forces, and poor, film is easy to fall off and is difficult to practical application and asks
Topic.There are intensity difference, electric leakage are big for these methods, it is difficult to stablize chemical conversion anode energize production and capacitor winding production the problems such as.
Patent CN 104919552A implements the manufacturing method of etching process to the epithelium through being sintered, but handles by soda acid, at environmental protection
Reason brings difficulty, exists simultaneously and is difficult to stablize the problems such as producing of energizing.
Summary of the invention
In order to overcome the defects of the prior art described above and insufficient, one aspect of the present invention provides a kind of Fabrication of High Specific Capacitance high intensity aluminium
The three-dimensional porous aluminum electric pole foil of electrolytic capacitor, the three-dimensional porous aluminum electric pole foil have high-intensitive and Fabrication of High Specific Capacitance, and high in satisfaction
The aluminium electrolutic capacitor electrode material of pressure and super-pressure.On the other hand provide it is a kind of by metal powder prepare this three
The method for tieing up porous aluminum electric pole foil.
Technical solution of the present invention on the one hand provide a kind of porous aluminum electric pole foil of novel three-dimensional, comprising Al foil substrate and by
The compound porous aluminium film that mixed powder is formed on Al foil substrate two sides, the overall thickness of the three-dimensional porous aluminum electric pole foil is 80 μm-
200μm。
The porous aluminum electric pole foil of the novel three-dimensional provided according to the above technical scheme, the voltage of the porous aluminum electric pole foil of novel three-dimensional
For 300-600V, bending times are 50-340 times, and specific volume is 0.70-2.55 μ F/cm2。
The porous aluminum electric pole foil of the novel three-dimensional provided according to the above technical scheme, Al foil substrate with a thickness of 20-100 μm,
Purity is not less than 99.92%.
The porous aluminum electric pole foil of the novel three-dimensional provided according to the above technical scheme, compound porous aluminium film single layer with a thickness of
20-100 μm, in other embodiments, compound porous aluminium film single layer with a thickness of 30 μm, 35 μm, 40 μm, 45 μm, 50 μm,
60 μm, 70 μm, 80 μm, 90 μm or 100 μm.
The porous aluminum electric pole foil of the novel three-dimensional provided according to the above technical scheme, the porous aluminum electric pole foil of novel three-dimensional are
It is prepared by way of metal-powder rolling, porosity 35%-45%.
The porous aluminum electric pole foil of the novel three-dimensional provided according to the above technical scheme, in mixed powder, by weight percentage,
95-99% is accounted for containing aluminium powder, aluminum fiber accounts for 0.5%-5%, and high dielectric oxide powder accounts for 0.05%-2%.It is added in the present invention
High dielectric oxide have the function of key even and support, can prevent aluminium powder because drafts increase it is severely deformed, ensure that simultaneously
Porosity.
The porous aluminum electric pole foil of the novel three-dimensional provided according to the above technical scheme is selected from aluminum or aluminum alloy powder containing aluminium powder
At least one of.
The porous aluminum electric pole foil of the novel three-dimensional provided according to the above technical scheme, high dielectric oxide powder are selected from Al2O3、
TiO2And at least one of barium titanate.
The porous aluminum electric pole foil of the novel three-dimensional provided according to the above technical scheme is single in subsequent actual production
Partial size is classified, other than price height in addition to being difficult to, and also generates a large amount of waste, increases the cost of production, therefore use in mixing process
Different under partial size is big, 20 μm maximum, 0.5 μm minimum, shape is different spindle, and bar shaped is cylindrical, threadiness and sheet.Though
So in this way collocation to slurry filtering and it is evenly dispersed bring problem, and have the tendency that reducing specific capacity, but the whole compound effect of thermalization
Fruit is obvious, is not susceptible to seriously be compacted, and porosity reduces and cracking phenomena, while greatling save production cost.Therefore one
The partial size containing aluminium powder is 1-20 μm in a little embodiments；In further embodiments, the partial size containing aluminium powder is 3-15 μm.Furthermore
The control to three-dimensional porous aluminum electric pole foil voltage also may be implemented in partial size by controlling powder, and usual diameter of particle reduces, obtains
To the voltage of three-dimensional porous aluminum electric pole foil can also reduce a bit.
The porous aluminum electric pole foil of the novel three-dimensional provided according to the above technical scheme, 3-10 μm of aluminum fiber diameter, length 1-500
μm；The porous aluminum electric pole foil of the novel three-dimensional provided according to the above technical scheme, high dielectric oxidation powder, purity are not less than
99.9%, 0.2-5 μm of granularity.
The porous aluminum electric pole foil of the novel three-dimensional provided according to the above technical scheme, three-dimensional porous aluminum electric pole foil are by that will mix
Powder is closed to be integrated on aluminium foil by extruding, thermalization processing, and be prepared by chemical conversion treatment.
On the other hand technical solution of the present invention provides a kind of preparation method of porous aluminum electric pole foil of above-mentioned novel three-dimensional,
The following steps are included:
1) aluminium powder, aluminum fiber and high dielectric oxide powder will be contained and be mixed into mixed powder；
2) mixed powder is dispersed in Al foil substrate two sides, and carries out compacting and forms closely packed porous foil；
3) by closely packed porous foil carry out thermalization processing, and by extrusion process control the porosity be 35%-45%,
With a thickness of 80 μm -200 μm, the porous aluminum electric pole foil of composite mesh is ultimately formed；
4) by thermalization, treated that porous aluminum electric pole foil carries out formation energy-endowing processing.
The method provided according to the above technical scheme in mixed powder, by weight percentage, accounts for 95- containing aluminium powder
99%, aluminum fiber accounts for 0.5%-5%, and high dielectric oxide powder accounts for 0.05%-2%；Aluminium wherein is selected from containing aluminium powder or aluminium closes
At least one of bronze end, high dielectric oxide powder are selected from Al2O3、TiO2And at least one of barium titanate.
The method provided according to the above technical scheme, the partial size containing aluminium powder are 1-20 μm；3-10 μm of aluminum fiber diameter, it is long
1-500 μm of degree；High dielectric oxidation powder, purity is not less than 99.9%, 0.2-5 μm of granularity.
The method provided according to the above technical scheme, compaction treatment are 50-300Kg to be pressed by chilling roller and controlling pressure；
The extrusion process is also to be pressed by chilling roller and carried out under the conditions of temperature is 300 DEG C, pressure is 10-20Kg.
Mixed powder is dispersed in aluminium base two sides and refers to its table of control by the method provided according to the above technical scheme
Surface roughness is no more than ± 8 μm.
The method provided according to the above technical scheme carries out thermalization processing to foil is squeezed, so that aluminium base and powder and powder
End is merged with powder directly heat, forms the porous aluminum electric pole foil of thermalization of secured porous network structure, the thermalization processing in the present invention
It is to be carried out under vacuum or inert gas conditions.
The method provided according to the above technical scheme, the temperature of thermalization processing are 550-670 DEG C, and the processing time is 1-
30min。
The method provided according to the above technical scheme, inert gas are selected from N2Or Ar2。
The method provided according to the above technical scheme, formation energy-endowing processing hydro-combination process in added with reproducibility be electrolysed
Matter.
The method provided according to the above technical scheme, the reproducibility electrolyte that adds in the hydro-combination process of formation energy-endowing processing
For hydrogen peroxide or citric acid, content 0.01%-0.5%；It is in embodiment at other, reproducibility electrolyte is hydrogen peroxide,
Its content 0.05%-0.10%.The surface stress of clad aluminum foil can be eliminated by increasing reducing substances in the treatment process of energizing
And residual decomposition object, increase clad aluminum foil particle linkage and ability.To thoroughly solve chemical conversion cracking, produce disconnected foil, greatly mention
High bending intensity.
Heretofore described " aluminium foil " is not limited to light foil, etched foil and Waste Acid From Hua Cheng Foil, preferably light foil.
Heretofore described " Al alloy powder " refer to purity 99.92% or more, D50 average grain diameter be 1-15 μm,
And the powder containing Si, Fe, Cu, Mn and Mg etc..
Originally unless explicitly stated otherwise in contrast, otherwise, all ranges that the present invention quotes include end value.For example, " described
The temperature of thermalization processing is 550-670 DEG C ", indicate that the range of reaction temperature T is 550 DEG C≤T≤670 DEG C.
Terminology used in the present invention "or" indicates that alternative can combine them if applicable, that is,
It says, term "or" includes each listed independent alternative and their combination.For example, " the reproducibility electrolyte
For hydrogen peroxide or citric acid " indicate reproducibility electrolyte can be hydrogen peroxide or citric acid one of, be also possible to one
Kind or more combination.
The beneficial effects of the present invention are:
The present invention provides a kind of novel three-dimensional porous aluminum electric pole foils, and the electrode foil is comprising Al foil substrate and by mixed powder
The compound porous aluminium film that body is formed on Al foil substrate two sides, is suitable for mesohigh and ultra-high voltage aluminum electrolytic capacitor is used, and has very
The characteristic of good mechanical performance and Fabrication of High Specific Capacitance, the compound porous aluminium film on the Al foil substrate is in process of production without cracking, without de-
It falls, has the characteristics that binding force is good.And it can realize quality stability of energizing.
The present invention provides a kind of preparation method of the porous aluminum electric pole foil of novel three-dimensional, this method is metal-powder rolling foil
Powder is uniformly distributed on aluminum substrates by material first, then chilling roller swaging is at closely packed porous foil, closely packed porous to this
Paillon carries out thermalization processing and forms the porous aluminum electric pole foil of composite mesh, and carries out formation energy-endowing to the clad aluminum foil, assigns in chemical conversion
It can carry out environmental-friendly reproducibility hydration-treated the stage, realization re-forms the modification of composite mesh structure, without again to more
Hole aluminum electric pole foil is etched, roughing in surface or reason of eliminating surface oxidation film thickness etc., guarantees the stabilization of production and high-strength
Degree requires, and forms the electrode foil for being suitable for the Fabrication of High Specific Capacitance high intensity of mesohigh and ultra-high voltage aluminum electrolytic capacitor.
Specific embodiment
As described below is the preferred embodiment of the present invention, and what the present invention was protected is not limited to following preferred implementation side
Formula.It should be pointed out that for those skilled in the art on the basis of the inventive concept, several deformations for making and
It improves, belongs to protection scope of the present invention.Raw material used in embodiment can be obtained through commercial channels.
Comparative example 1
By annealed treated the soft smooth foil of 130 μ m-thicks, tunnel hole is formed using known etch process, then through changing
At-obtained the electrode foil of anodic oxidation.This technique is to be largely used to the system of the electrode foil of aluminium electrolutic capacitor production currently on the market
Make method.
Comparative example 2
The aluminium powder for being 3 μm by average grain diameter D50,30 μm of Al foil substrate is pushed to by powder spray or screw pump
On, monoplanar surface uniformity is controlled by scraper, so that powder surface roughness is no more than ± 8 μm, passes through chilling roller pressure, control pressure
Power is 100Kg, preliminary consolidation aluminium powder；Then, the aluminium foil 800mm of surface cladding aluminium powder is under the support of ceramic roller, in argon
630 DEG C of thermalization processing are carried out under gas shielded, and when being cooled to 300 DEG C, the porosity and thickness, preferably pressure are controlled by cold pressing roller
For 15Kg, the porosity 40% repeats above-mentioned process in compound 50 μm of the aluminium powder of the another side of aluminium base and obtains overall thickness
The compound porous foil of 130 μm of thermalization；Conventional nitration mixture is carried out to thermalization composite insulating foil and energizes that obtain Fabrication of High Specific Capacitance high-intensitive for chemical synthesis technology
Electrode foil.
Embodiment 1
The aluminium powder for being 3 μm by average grain diameter D50,30 μm of Al foil substrate is pushed to by powder spray or screw pump
On, monoplanar surface uniformity is controlled by scraper, so that powder surface roughness is no more than ± 8 μm, passes through chilling roller pressure 1, control
Pressure is 200Kg, and preliminary consolidation aluminium powder controls single side with a thickness of 50 μm；Then the aluminium foil 800mm of surface cladding aluminium powder
Under the support of ceramic roller, 570 DEG C of thermalization processing are carried out under protection of argon gas, when being cooled to 300 DEG C, are controlled by cold pressing roller 2
The porosity and thickness processed, preferably pressure are 20Kg, the porosity 40%；Above-mentioned process is repeated, it is compound in the another side of aluminium base
50 μm of aluminium powder obtains 130 μm of overall thickness of the compound porous foil of thermalization, carries out nitration mixture to the compound porous aluminium foil of thermalization and energizes,
In hydro-combination process, be hydrated be added in slot 0.05% hydrogen peroxide, carry out conventional nitration mixture chemical synthesis technology of energizing later and obtain high ratio
Hold high-intensitive electrode foil.
Embodiment 2
The aluminium powder for being 5 μm by average grain diameter D50,30 μm of Al foil substrate is pushed to by powder spray or screw pump
On, monoplanar surface uniformity is controlled by scraper, so that powder surface roughness is no more than ± 8 μm, passes through chilling roller pressure 1, control
Pressure is 150Kg, preliminary consolidation aluminium powder；Then, surface cladding aluminium powder aluminium foil 800mm under the support of ceramic roller,
Argon gas protection is lower to carry out 570 DEG C of thermalization processing, when being cooled to 300 DEG C, controls the porosity and thickness by cold pressing roller 2, preferably
Pressure is 20Kg, the porosity 35%；Above-mentioned process is repeated, in compound 50 μm of the aluminium powder of the another side of aluminium base, is obtained total
The compound porous foil of the thermalization that 130 μm of thickness；Nitration mixture is carried out to thermalization composite insulating foil to energize, and in hydro-combination process, is hydrated in slot and is added
0.05% hydrogen peroxide carries out conventional nitration mixture chemical synthesis technology of energizing later and obtains the electrode foil of Fabrication of High Specific Capacitance high intensity.
Embodiment 3
The aluminium powder for being 3 μm by average grain diameter D50,30 μm of Al foil substrate is pushed to by powder spray or screw pump
On, monoplanar surface uniformity is controlled by scraper, so that powder surface roughness is no more than ± 8 μm, passes through chilling roller pressure 1, control
Pressure is 100Kg, preliminary consolidation aluminium powder；Then, surface cladding aluminium powder aluminium foil 800mm under the support of ceramic roller,
Argon gas protection is lower to carry out 630 DEG C of thermalization processing, when being cooled to 300 DEG C, controls the porosity and thickness by cold pressing roller 2, preferably
Pressure is 15Kg, and the porosity 40% repeats above-mentioned process, in compound 50 μm of the aluminium powder of the another side of aluminium base, is obtained total
The compound porous foil of the thermalization that 130 μm of thickness；Nitration mixture is carried out to thermalization composite insulating foil to energize, and in hydro-combination process, is hydrated in slot and is added
0.05% hydrogen peroxide carries out conventional nitration mixture chemical synthesis technology of energizing later and obtains the electrode foil of Fabrication of High Specific Capacitance high intensity.
Embodiment 4
It is 3 μm of aluminium powder by average grain diameter D50, the aluminum fiber that diameter is 3-10 μm, length is 10-100 μm is and average
The high dielectric oxidation powder that partial size is 0.5-2 μm is mixed into uniform mixing by dry-powder mixer, and three's weight ratio is 95:4:1；
Mixing is pushed on 30 μm of Al foil substrate by screw pump again, monoplanar surface uniformity is controlled by scraper, so that powder
Surface roughness is no more than ± 8 μm, and by chilling roller pressure 1, control pressure is 100Kg, preliminary consolidation mixing；Then, surface is wrapped
The aluminium foil 800mm of aluminium mixing is covered under the support of ceramic roller, is carried out 570 DEG C of thermalization processing under protection of argon gas, is cooled to 300
DEG C when, the porosity and thickness are controlled by cold pressing roller 2, preferably pressure is 15Kg, and the porosity 45% repeats above-mentioned process,
Compound 50 μm of the aluminium powder of the another side of aluminium base obtains 130 μm of overall thickness of the compound porous foil of thermalization；To thermalization composite insulating foil into
Row nitration mixture is energized, and in hydro-combination process, is hydrated the hydrogen peroxide of addition 0.05% in slot, and the conventional nitration mixture of progress later, which is energized, is melted into work
Skill obtains the electrode foil of Fabrication of High Specific Capacitance high intensity.
Embodiment 5
It is 3 μm of aluminium powder by average grain diameter D50, the aluminum fiber that diameter is 3-10 μm, length is 10-100 μm is and average
The high dielectric oxidation powder that partial size is 0.5-2 μm is mixed into uniform mixing by dry-powder mixer, and the weight ratio of three is 95:4:
1；Mixing is pushed on 30 μm of Al foil substrate by screw pump again, monoplanar surface uniformity is controlled by scraper, so that powder
Body surface surface roughness is no more than ± 8 μm, and by chilling roller pressure 1, control pressure is 100Kg, preliminary consolidation mixing；Then, surface
The aluminium foil 800mm of aluminium mixing is coated under the support of ceramic roller, 630 DEG C of thermalization processing is carried out under protection of argon gas, is cooled to
At 300 DEG C, the porosity and thickness are controlled by cold pressing roller 2, preferably pressure is 15Kg, and the porosity 40% repeats above-mentioned process,
In compound 50 μm of the aluminium powder of the another side of aluminium base, 130 μm of overall thickness of the compound porous foil of thermalization is obtained；To thermalization composite insulating foil
Nitration mixture is carried out to energize, in hydro-combination process, be hydrated be added in slot 0.05% hydrogen peroxide, carry out conventional nitration mixture later and energize chemical conversion
Technique obtains the electrode foil of Fabrication of High Specific Capacitance high intensity.
Embodiment 6
It is 3 μm of aluminium powder by average grain diameter D50, the aluminum fiber that diameter is 3-10 μm, length is 10-100 μm is and average
The high dielectric oxidation powder that partial size is 0.5-2 μm is mixed into uniform mixing by dry-powder mixer, and the weight ratio of three is 96:3:
1；Mixing is pushed on 30 μm of Al foil substrate by screw pump again, monoplanar surface uniformity is controlled by scraper, so that powder
Body surface surface roughness is no more than ± 8 μm, and by chilling roller pressure 1, control pressure is 100Kg, preliminary consolidation mixing；Then, surface
The aluminium foil 800mm of aluminium mixing is coated under the support of ceramic roller, 600 DEG C of thermalization processing is carried out under protection of argon gas, is cooled to
At 300 DEG C, the porosity and thickness are controlled by cold pressing roller 2, preferably pressure is 15Kg, and the porosity 40% repeats above-mentioned process,
In compound 50 μm of the aluminium powder of the another side of aluminium base, 130 μm of overall thickness of the compound porous foil of thermalization is obtained；To thermalization composite insulating foil
Nitration mixture is carried out to energize, in hydro-combination process, be hydrated be added in slot 0.05% hydrogen peroxide, carry out conventional nitration mixture later and energize chemical conversion
Technique obtains the electrode foil of Fabrication of High Specific Capacitance high intensity.
Embodiment 7
The aluminium powder for being 3 μm by average grain diameter D50, the aluminum fiber and be averaged that diameter is 3-10 μm, length is 10-100 μm
The high dielectric oxidation powder that partial size is 0.5-2 μm is mixed into uniform mixing by dry-powder mixer, and three's weight ratio is 96:3:1；
Mixing is pushed on 30 μm of Al foil substrate by screw pump again, monoplanar surface uniformity is controlled by scraper, so that powder
Surface roughness is no more than ± 8 μm, and by chilling roller pressure 1, control pressure is 300Kg, preliminary consolidation mixing；Then, surface is wrapped
The aluminium foil 800mm of aluminium mixing is covered under the support of ceramic roller, is carried out 630 DEG C of thermalization processing under protection of argon gas, is cooled to 300
DEG C when, the porosity and thickness are controlled by cold pressing roller 2, preferably pressure is 10Kg, and the porosity 40% repeats above-mentioned process,
Compound 50 μm of the aluminium powder of the another side of aluminium base obtains 130 μm of overall thickness of the compound porous foil of thermalization；To thermalization composite insulating foil into
Row nitration mixture is energized, and in hydro-combination process, is hydrated the hydrogen peroxide of addition 0.05% in slot, and the conventional nitration mixture of progress later, which is energized, is melted into work
Skill obtains the electrode foil of Fabrication of High Specific Capacitance high intensity.
Embodiment 8
It is 3 μm of aluminium powder by average grain diameter D50, the aluminum fiber that diameter is 3-10 μm, length is 10-100 μm is and average
Partial size is mixed into uniform mixing by dry-powder mixer for 0.5-2 μm high dielectric oxidation powder, and the weight ratio of three is 96:2:2；
Mixing is pushed on 30 μm of Al foil substrate by screw pump again, monoplanar surface uniformity is controlled by scraper, so that powder
Surface roughness is no more than ± 8 μm, and by chilling roller pressure 1, control pressure is 250Kg, preliminary consolidation mixing；Then, surface is wrapped
The aluminium foil 800mm of aluminium mixing is covered under the support of ceramic roller, is carried out 630 DEG C of thermalization processing under protection of argon gas, is cooled to 300
DEG C when, the porosity and thickness are controlled by cold pressing roller 2, preferably pressure is 10Kg, and the porosity 45% repeats above-mentioned process,
Compound 50 μm of the aluminium powder of the another side of aluminium base obtains 130 μm of overall thickness of the compound porous foil of thermalization；To thermalization composite insulating foil into
Row nitration mixture is energized, and in hydro-combination process, is hydrated the hydrogen peroxide of addition 0.05% in slot, and the conventional nitration mixture of progress later, which is energized, is melted into work
Skill obtains the electrode foil of Fabrication of High Specific Capacitance high intensity.
Embodiment 9
The aluminium powder for being 3 μm by average grain diameter D50, the aluminum fiber that diameter is 3-10 μm, length is 10-100 μm, average grain
The high dielectric oxidation powder that diameter is 0.5-2 μm is mixed into uniform mixing by dry-powder mixer, and the weight ratio of three is 96:2:2；
Mixing is pushed on 30 μm of Al foil substrate by screw pump again, monoplanar surface uniformity is controlled by scraper, so that powder
Surface roughness is no more than ± 8 μm, and by chilling roller pressure 1, control pressure is 50Kg, preliminary consolidation mixing；Then, surface is coated
The aluminium foil 800mm of aluminium mixing carries out 640 DEG C of thermalization processing under protection of argon gas, is cooled to 300 DEG C under the support of ceramic roller
When, the porosity and thickness are controlled by cold pressing roller 2, preferably pressure is 10Kg, and the porosity 35% repeats above-mentioned process, in aluminium
Compound 50 μm of the aluminium powder of the another side of substrate obtains 130 μm of overall thickness of the compound porous foil of thermalization；Thermalization composite insulating foil is carried out
Nitration mixture is energized, in hydro-combination process, be hydrated be added in slot 0.05% hydrogen peroxide, carry out conventional nitration mixture later and energize chemical synthesis technology
Obtain the electrode foil of Fabrication of High Specific Capacitance high intensity.
Embodiment 10
The aluminium powder for being 3 μm by average grain diameter D50, the aluminum fiber that diameter is 3-10 μm, length is 10-100 μm, average grain
The high dielectric oxidation powder that diameter is 0.5-2 μm is mixed into uniform mixing by dry-powder mixer, and the weight ratio of three is 96:2:2；
Mixing is pushed on 30 μm of Al foil substrate by screw pump again, monoplanar surface uniformity is controlled by scraper, so that powder
Surface roughness is no more than ± 8 μm, and by chilling roller pressure 1, control pressure is 100Kg, preliminary consolidation mixing；Then, surface is wrapped
The aluminium foil 800mm of aluminium mixing is covered under the support of ceramic roller, is carried out 630 DEG C of thermalization processing under protection of argon gas, is cooled to 300
DEG C when, the porosity and thickness are controlled by cold pressing roller 2, preferably pressure is 10Kg, and the porosity 45% repeats above-mentioned process,
Compound 50 μm of the aluminium powder of the another side of aluminium base obtains 130 μm of overall thickness of the compound porous foil of thermalization；To thermalization composite insulating foil into
Row nitration mixture is energized, and in hydro-combination process, is hydrated the hydrogen peroxide of addition 0.1% in slot, and the conventional nitration mixture of progress later, which is energized, is melted into work
Skill obtains the electrode foil of Fabrication of High Specific Capacitance high intensity.
Embodiment 11
The aluminium powder for being 3 μm by average grain diameter D50, the aluminum fiber that diameter is 3-10 μm, length is 10-100 μm, average grain
0.5-2 μm of diameter of high dielectric oxidation powder is mixed into uniform mixing by dry-powder mixer, and the weight ratio of three is 96:2:2；Again
Mixing is pushed on 30 μm of Al foil substrate by screw pump, monoplanar surface uniformity is controlled by scraper, so that powder table
Surface roughness is no more than ± 8 μm, and by chilling roller pressure 1, control pressure is 100Kg, preliminary consolidation mixing；Then, surface is coated
The aluminium foil 800mm of aluminium mixing carries out 630 DEG C of thermalization processing under protection of argon gas, is cooled to 300 DEG C under the support of ceramic roller
When, the porosity and thickness are controlled by cold pressing roller 2, preferably pressure is 10Kg, and the porosity 45% repeats above-mentioned process, in aluminium
Compound 50 μm of the aluminium powder of the another side of substrate obtains 130 μm of overall thickness of the compound porous foil of thermalization；Thermalization composite insulating foil is carried out
Nitration mixture is energized, in hydro-combination process, be hydrated be added in slot 0.4% hydrogen peroxide, carry out conventional nitration mixture later and energize chemical synthesis technology
Obtain the electrode foil of Fabrication of High Specific Capacitance high intensity.
Embodiment 12
The aluminium powder for being 5 μm by average grain diameter D50, the aluminum fiber that diameter is 3-10 μm, length is 10-100 μm, average grain
The high dielectric oxidation powder that diameter is 0.5-2 μm is mixed into uniform mixing by dry-powder mixer, and the weight ratio of three is 96:2:2；
Mixing is pushed on 30 μm of Al foil substrate by screw pump again, monoplanar surface uniformity is controlled by scraper, so that powder
Surface roughness is no more than ± 8 μm, and by chilling roller pressure 1, control pressure is 100Kg, preliminary consolidation mixing；Then, surface is wrapped
The aluminium foil 800mm of aluminium mixing is covered under the support of ceramic roller, is carried out 630 DEG C of thermalization processing under protection of argon gas, is cooled to 300
DEG C when, the porosity and thickness are controlled by cold pressing roller 2, preferably pressure is 10Kg, and the porosity 35% repeats above-mentioned process,
Compound 50 μm of the aluminium powder of the another side of aluminium base obtains 130 μm of overall thickness of the compound porous foil of thermalization；To thermalization composite insulating foil into
Row nitration mixture is energized, and in hydro-combination process, is hydrated the hydrogen peroxide of addition 0.1% in slot, and the conventional nitration mixture of progress later, which is energized, is melted into work
Skill obtains the electrode foil of Fabrication of High Specific Capacitance high intensity.
Embodiment 13
The aluminium powder for being 5 μm by average grain diameter D50, the aluminum fiber that diameter is 3-10 μm, length is 10-100 μm, average grain
The high dielectric oxidation powder that diameter is 0.5-2 μm is mixed into uniform mixing by dry-powder mixer, and the weight ratio of three is 96:2:2；
Mixing is pushed on 30 μm of Al foil substrate by screw pump again, monoplanar surface uniformity is controlled by scraper, so that powder
Surface roughness is no more than ± 8 μm, and by chilling roller pressure 1, control pressure is 100Kg, preliminary consolidation mixing；Then, surface is wrapped
The aluminium foil 800mm of aluminium mixing is covered under the support of ceramic roller, is carried out 630 DEG C of thermalization processing under protection of argon gas, is cooled to 300
DEG C when, the porosity and thickness are controlled by cold pressing roller 2, preferably pressure is 10Kg, and the porosity 35% repeats above-mentioned process,
Compound 50 μm of the aluminium powder of the another side of aluminium base obtains 130 μm of overall thickness of the compound porous foil of thermalization；To thermalization composite insulating foil into
Row nitration mixture is energized, and in hydro-combination process, is hydrated the hydrogen peroxide of addition 0.4% in slot, and the conventional nitration mixture of progress later, which is energized, is melted into work
Skill obtains the electrode foil of Fabrication of High Specific Capacitance high intensity.
Note: the test method of every paillon performance parameter is carried out by SJ/T 11140-1997 standard.
By above data it is found that three-dimensional porous aluminum electric pole foil provided by the invention has the property such as Fabrication of High Specific Capacitance and high intensity
Can, and the compound porous aluminium film on Al foil substrate has the characteristics that binding force is good in process of production without cracking, without falling off.This
By using hydrogen peroxide hydration-treated in the formation energy-endowing stage in invention, lead to the folding of three-dimensional porous aluminum electric pole foil finally prepared
Curved intensity and specific volume greatly improve.The high dielectric oxide added in the present invention simultaneously has the function of key even and supports, and can prevent
Only aluminium powder is severely deformed because drafts increases, while ensure that porosity.
Claims (10)
1. a kind of porous aluminum electric pole foil of novel three-dimensional is answered comprising Al foil substrate and by mixed powder what Al foil substrate two sides was formed
Close porous aluminium, which is characterized in that the overall thickness of the three-dimensional porous aluminum electric pole foil is 80 μm -200 μm.
2. the porous aluminum electric pole foil of novel three-dimensional according to claim 1, which is characterized in that the three-dimensional porous aluminum electric pole foil
Voltage be 300-600V, bending times be 50-340 return, specific volume be 0.70-2.55 μ F/cm2。
3. the porous aluminum electric pole foil of novel three-dimensional according to claim 1, which is characterized in that the Al foil substrate with a thickness of
20-100 μm, purity is not less than 99.92%；The compound porous aluminium film single layer with a thickness of 20-100 μm.
4. the porous aluminum electric pole foil of novel three-dimensional according to claim 1, which is characterized in that the novel three-dimensional porous aluminum electricity
Pole foil is prepared by way of metal-powder rolling, porosity 35%-45%.
5. the porous aluminum electric pole foil of novel three-dimensional according to claim 1, which is characterized in that in the mixed powder, by weight
Percentages are measured, account for 95-99% containing aluminium powder, aluminum fiber accounts for 0.5%-5%, and high dielectric oxide powder accounts for 0.05%-2%；
Described to be selected from least one of aluminum or aluminum alloy powder containing aluminium powder, the high dielectric oxide powder is selected from Al2O3、TiO2
And at least one of barium titanate.
6. the porous aluminum electric pole foil of novel three-dimensional according to claim 5, which is characterized in that the partial size containing aluminium powder is
1-20μm；3-10 μm of the aluminum fiber diameter, 1-500 μm of length；The high dielectric oxidation powder, purity are not less than
99.9%, 0.2-5 μm of granularity.
7. a kind of preparation method of the porous aluminum electric pole foil of novel three-dimensional as described in claim 1-6, which is characterized in that including with
Lower step:
1) aluminium powder, aluminum fiber and high dielectric oxide powder will be contained and be mixed into mixed powder；
2) mixed powder is dispersed in Al foil substrate two sides, and carries out compacting and forms closely packed porous foil；
3) closely packed porous foil is subjected to thermalization processing, and controlling the porosity by extrusion process is 35%-45%, thickness
It is 80 μm -200 μm, ultimately forms the porous aluminum electric pole foil of composite mesh；
4) by thermalization, treated that porous aluminum electric pole foil carries out formation energy-endowing processing.
8. preparation method according to claim 7, which is characterized in that the compaction treatment is to be pressed by chilling roller and control pressure
Power is 50-300Kg；The extrusion process is pressed in temperature by chilling roller and is 300 DEG C, carries out under the conditions of pressure is 10-20Kg.
9. preparation method according to claim 7, which is characterized in that described that mixed powder is dispersed in aluminium base two
Face refers to that control surface roughness is no more than ± 8 μm；The thermalization processing is carried out under vacuum or inert gas conditions；
The temperature of the thermalization processing is 550-670 DEG C, and the processing time is 1-30min；The inert gas is selected from N2Or Ar2。
10. preparation method according to claim 7, which is characterized in that add in the hydro-combination process of the formation energy-endowing processing
Added with reproducibility electrolyte；The reproducibility electrolyte is hydrogen peroxide or citric acid, content 0.01%-0.5%；Or it is described also
Originality electrolyte is hydrogen peroxide, content 0.05%-0.10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810913489.XA CN109036852B (en) | 2018-08-13 | 2018-08-13 | Three-dimensional porous aluminum electrode foil and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810913489.XA CN109036852B (en) | 2018-08-13 | 2018-08-13 | Three-dimensional porous aluminum electrode foil and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109036852A true CN109036852A (en) | 2018-12-18 |
| CN109036852B CN109036852B (en) | 2020-09-18 |
Family
ID=64632886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810913489.XA Active CN109036852B (en) | 2018-08-13 | 2018-08-13 | Three-dimensional porous aluminum electrode foil and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109036852B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111360264A (en) * | 2020-05-11 | 2020-07-03 | 中南大学 | Method for manufacturing porosity-adjustable foamed aluminum electrode material |
| CN111627714A (en) * | 2020-05-28 | 2020-09-04 | 西安交通大学 | Preparation method of porous anode aluminum foil with multi-stage mixed structure |
| CN114523112A (en) * | 2021-12-30 | 2022-05-24 | 浙江洪量新材科技有限公司 | Porous electrode foil and preparation process thereof |
| CN115116753A (en) * | 2022-07-05 | 2022-09-27 | 新疆众和股份有限公司 | Aluminum electrode foil and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63291918A (en) * | 1987-05-25 | 1988-11-29 | Kanegafuchi Chem Ind Co Ltd | Curing composition |
| JPH0291918A (en) * | 1988-09-29 | 1990-03-30 | Nippon Steel Corp | Electrode material for electrolytic capacitor |
| JPH09306791A (en) * | 1996-05-13 | 1997-11-28 | Matsushita Electric Ind Co Ltd | Manufacture of solid electrolytic capacitor |
| JP2008098279A (en) * | 2006-10-10 | 2008-04-24 | Toyo Aluminium Kk | Electrode material for aluminum electrolytic capacitor, and its manufacturing method |
| CN101651048A (en) * | 2009-06-23 | 2010-02-17 | 吴江飞乐天和电子材料有限公司 | Forming method of electrode foil of aluminum electrolytic capacitor |
| CN103688327A (en) * | 2011-07-15 | 2014-03-26 | 东洋铝株式会社 | Electrode material for aluminum electrolytic capacitor, and method for producing same |
| CN104094370A (en) * | 2012-02-10 | 2014-10-08 | 东洋铝株式会社 | Method for manufacturing electrode material for aluminum electrolytic capacitor |
| CN105393320A (en) * | 2013-08-05 | 2016-03-09 | 东洋铝株式会社 | Electrode material for aluminum electrolytic capacitor, and production method thereof |
| CN105874549A (en) * | 2013-12-27 | 2016-08-17 | 东洋铝株式会社 | Electrode foil for aluminum electrolytic capacitor and production method for same |
| CN107967996A (en) * | 2017-11-15 | 2018-04-27 | 广西贺州市桂东电子科技有限责任公司 | A kind of chemical synthesizing method of mash welder capacitor anode foils |
-
2018
- 2018-08-13 CN CN201810913489.XA patent/CN109036852B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63291918A (en) * | 1987-05-25 | 1988-11-29 | Kanegafuchi Chem Ind Co Ltd | Curing composition |
| JPH0291918A (en) * | 1988-09-29 | 1990-03-30 | Nippon Steel Corp | Electrode material for electrolytic capacitor |
| JPH09306791A (en) * | 1996-05-13 | 1997-11-28 | Matsushita Electric Ind Co Ltd | Manufacture of solid electrolytic capacitor |
| JP2008098279A (en) * | 2006-10-10 | 2008-04-24 | Toyo Aluminium Kk | Electrode material for aluminum electrolytic capacitor, and its manufacturing method |
| CN101651048A (en) * | 2009-06-23 | 2010-02-17 | 吴江飞乐天和电子材料有限公司 | Forming method of electrode foil of aluminum electrolytic capacitor |
| CN103688327A (en) * | 2011-07-15 | 2014-03-26 | 东洋铝株式会社 | Electrode material for aluminum electrolytic capacitor, and method for producing same |
| CN104094370A (en) * | 2012-02-10 | 2014-10-08 | 东洋铝株式会社 | Method for manufacturing electrode material for aluminum electrolytic capacitor |
| CN105393320A (en) * | 2013-08-05 | 2016-03-09 | 东洋铝株式会社 | Electrode material for aluminum electrolytic capacitor, and production method thereof |
| CN105874549A (en) * | 2013-12-27 | 2016-08-17 | 东洋铝株式会社 | Electrode foil for aluminum electrolytic capacitor and production method for same |
| CN107967996A (en) * | 2017-11-15 | 2018-04-27 | 广西贺州市桂东电子科技有限责任公司 | A kind of chemical synthesizing method of mash welder capacitor anode foils |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111360264A (en) * | 2020-05-11 | 2020-07-03 | 中南大学 | Method for manufacturing porosity-adjustable foamed aluminum electrode material |
| CN111627714A (en) * | 2020-05-28 | 2020-09-04 | 西安交通大学 | Preparation method of porous anode aluminum foil with multi-stage mixed structure |
| CN111627714B (en) * | 2020-05-28 | 2021-08-13 | 西安交通大学 | Preparation method of porous anode aluminum foil with multi-stage mixed structure |
| CN114523112A (en) * | 2021-12-30 | 2022-05-24 | 浙江洪量新材科技有限公司 | Porous electrode foil and preparation process thereof |
| CN114523112B (en) * | 2021-12-30 | 2024-03-22 | 浙江洪量新材科技有限公司 | Porous electrode foil and preparation process thereof |
| CN115116753A (en) * | 2022-07-05 | 2022-09-27 | 新疆众和股份有限公司 | Aluminum electrode foil and preparation method and application thereof |
| CN115116753B (en) * | 2022-07-05 | 2023-11-28 | 新疆众和股份有限公司 | Aluminum electrode foil and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109036852B (en) | 2020-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109036852A (en) | A kind of porous aluminum electric pole foil of novel three-dimensional and preparation method thereof | |
| AU2004203208B2 (en) | Process for producing niobium suboxide | |
| US8562765B2 (en) | Process for heat treating metal powder and products made from the same | |
| AU2010212675B2 (en) | A method for producing metal powders | |
| AU2010201394B2 (en) | Process for producing capacitors | |
| IL203658A (en) | Solid electrolyte capacitor anodes made from tantalum | |
| US20040238848A1 (en) | Composite titanium oxide film and method for formation thereof and titanium electrolytic capacitor | |
| CN114751743B (en) | Modified Ni-Ti-Ta dielectric material for multilayer ceramic capacitor and low-temperature preparation method thereof | |
| JP2000286154A (en) | Manufacture of solid-state electrolytic capacitor | |
| JP2004018966A (en) | Method for forming titanium oxide coating film and titanium electrolytic capacitor | |
| JP2009152273A (en) | Porous electrode for electrolytic capacitor, and manufacturing method thereof | |
| KR20020062579A (en) | Niobium powder and anode for solid electrolytic capacitors | |
| EP1529583A1 (en) | Niobium powder, anode for solid electrolytic capacitor and solid electrolytic capacitor | |
| AU2012233029A1 (en) | Process for producing capacitors | |
| JPS63268233A (en) | Manufacture of solid electrolytic capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201015 Address after: 2 / F, no.8-1, Qianxi Road, Taozhu street, Zhuji City, Shaoxing City, Zhejiang Province Patentee after: Zhejiang Hongliu New Material Technology Co., Ltd Address before: 322000 No. 321 Wangwang Road, Beiyuan Street, Yiwu City, Jinhua City, Zhejiang Province Patentee before: ZHEJIANG HUAYI RUIDONG NEW MATERIAL Co.,Ltd. |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 311899 no.8-1-1, Qianxi Road, Taozhu street, Zhuji City, Shaoxing City, Zhejiang Province Patentee after: Zhejiang Hongliang New Material Technology Co.,Ltd. Address before: 2 / F, no.8-1, Qianxi Road, Taozhu street, Zhuji City, Shaoxing City, Zhejiang Province Patentee before: Zhejiang Hongliu New Material Technology Co., Ltd |