CN101442113A - Three-dimensional pore space electrode for accumulator - Google Patents
Three-dimensional pore space electrode for accumulator Download PDFInfo
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- CN101442113A CN101442113A CNA2007101584378A CN200710158437A CN101442113A CN 101442113 A CN101442113 A CN 101442113A CN A2007101584378 A CNA2007101584378 A CN A2007101584378A CN 200710158437 A CN200710158437 A CN 200710158437A CN 101442113 A CN101442113 A CN 101442113A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a three-dimensional pore electrode for storage batteries, which is characterized in that an electrode pole plate consists of a three-dimensional net matrix formed in a way that the adding amount of non-metallic materials accounts for 10 to 90 percent of the volume of active matter; and the active matter is inlaid in meshes, so as to form a porous electrode matrix with a three-dimensional pore structure. The preparation of the electrode comprises the following steps: framework material, microporous material and adhesive material are mechanically mixed in the mixture ratio, put into mold, hot-pressed for 2 to 5 minutes at a temperature between 100 and 300 DEG C, knocked out, put into a heating furnace, fired to be 590 to 74 microns of microporous material as the three-dimensional net matrix on standby; lead or lead dioxide is inlaid into the meshes of the three-dimensional net matrix through a mechanical coating-filling mode; and a conducting layer is attached to three-dimensional matrix material by a chemical plating method, put into an oxygen furnace, supplied with oxygen and treated for 15 to 60 minutes. The three-dimensional pore electrode has the advantages that the utilization ratio of the active matter is greatly improved by increasing the surface area of micropores, and a storage battery made of the electrode has high specific energy, high power, long service life, high discharge rate and quick charge capability.
Description
Technical field
The invention belongs to the secondary power supply technical field, relate to accumulator positive negative electrode (pole plate) constituent material, particularly relate to the three-dimensional porous electrode constituent material in the storage battery, and the method for making this three-dimensional pore space electrode.
Background technology
Storage battery also claims secondary cell, is that electric energy-chemical energy-electric energy is stored reforming unit.Its kind is a lot, and lead-acid battery, ickel-cadmium cell, Ni-MH battery, lithium ion battery, nickel-zinc cell, lithium polymer battery and ultracapacitor or the like are arranged.Lead acid accumulator has become widely used in the world secondary cell through the development and perfection in over one hundred year, dominates in the secondary cell field.
Both at home and abroad the industrialized mode of production of polar plate of lead acid storage battery has two kinds, and a kind of is that to be coated with cream flat, and a kind of is tubulose powder filling formula.Paste spread type technology is that materials such as lead powder, water, sulfuric acid, additive are made lead plaster through special process, and it is coated on the grid, constitutes the basic material of active material, then through changing into the generation active material.The pole plate that makes is thinner, and battery efficiency is higher, and theoretic throat should be less than 2mm, and utilance can keep 30%---and 35%.Tubulose powder filling formula is with lead powder or makes plumbous particle (active matter) through special process and pack in the pipe that makes that postmenstruation, PROCESS FOR TREATMENT will be made battery in its battery case of packing into.The lead pipe theoretical diameter is less than 6mm, and utilance can keep 35～42%, and this structure mostly is used in than in the macrocell, and compact battery does not also have the battery of this structure.No matter be into cream or tubulation, its final purpose all is to make to constitute between active material particle, particle and the particle to form maximum surface area, has good guarantor's acidity, and the electrochemical reaction of battery is fully carried out, and reaches the purpose that improves battery performance.But the problem that lead acid accumulator self exists still is more,, problems such as specific energy low, life-span short, dark charging and discharging capabilities difference lower as active material utilization.Done a large amount of work for the performance various countries of improving lead acid accumulator, constantly dissolved in new technology from each side such as material, structure, technologies.
The battery manufacturing technology is fabricated to core with electrode, and general requirement is good electrical conductivity to be arranged, enough big surface area is arranged, the reaction medium that enough carries out electrochemical reaction is arranged, and the lead acid accumulator reaction medium is a sulfuric acid.Electrode with these advantages can make accumulator property, obviously improves as indexs such as active material utilization, specific energy, capacity, dark charging and discharging capabilities.For realizing this goal, over more than 100 year, numerous experts, scholar have carried out a large amount of research and experiments at the improvement of the electrode manufacturing method of lead acid accumulator, since two thousand the U.S., Japan disclose a large amount of patents in succession, and major part is to improve electrode performance in the domestic disclosed multinomial patent, and the characteristics of these patents are to continue to use the improvement that the traditional storage battery manufacturing equipment that possesses industry size, material, technology etc. are carried out.
In addition, do not adopt traditional manufacturing equipment, technology, the patent that looks for another way also has report, " porous electrode and manufacture method thereof " as the U.S., be that a large amount of cadmiums are fused in the lead, the cooling after-baking makes cadmium crystallization again, and the cadmium that exceeds the solubility part is come out with the sulfuric acid electrolyte electrolysis, form porous electrode, increase the long-pending purpose of polar board surface to reach." Lead Crystal Storage Cell manufacture method " patent utilizes cadmium at anode-catalyzed generation β one P b0 2, and cadmium is dissolved away by sulfuric acid, produces the effect of pore-creating on pole plate, and it is long-pending to improve polar board surface.This technical matters is made complicated, the cost of manufacture height, and can only be used for lead-acid battery.The patent No. is to propose in 95109703.2 " polar plate of lead acid storage battery and the manufacture methods thereof " lead is made into plumbous fiber and plumbous synthetic fibers, with these made battery pole plates, improves battery performance.The change of this class material prescription is spread though help electrolyte, does not effectively improve to make the long-pending increase of micropore surface.
Summary of the invention
The objective of the invention is to improve the formation of conventional batteries electrode material, provide a kind of high specific energy, high power, long-life, anti-overdischarge and battery terminal (pole plate), particularly lead acid accumulator that can quick charge with three-diemsnional electrode and manufacture method thereof based on metal.Nonmetallic materials have been widely applied in invention, and are long-pending by increasing micropore surface, increased substantially the active matter utilance, and electrode is thickened to 2-3 times of present thickness, reduce cost, and enhance productivity.
The present invention mainly is for storage battery provides improved electrode, and kind electrode is widely applied nonmetallic materials, and nonmetallic materials are prefabricated into the three-dimensional pore space structural matrix with good electric conductivity, active matter is embedded in the three-D pore structure again.The present invention includes grid, three-dimension hole matrix and active matter, its technical characterstic is: the formation of this electrode pad is 10～90% three dimensional network matrixes that form that account for the active matter volume with the nonmetallic materials addition content, active matter is embedded in the mesh, obtains having the porous electrode matrix of three-dimensional pore space structure.The preferred amounts that this three-dimensional pore space electrode for accumulator, the addition content of used nonmetallic materials account for the active matter volume is 20～60%.
Electrode matrix of the present invention mainly is made of TPO framework material, poromerics and binding material, and the weight ratio of three kinds of materials is 10～20:3～10:1, and the micro-pore diameter of three-dimensional porous electrode matrix is 590～74 microns.Framework material is selected polyethylene, polytetrafluoroethylene, high density polyethylene (HDPE), polypropylene for use; Poromerics is selected zeolite, perlite, active carbon for use; Binding material is selected sodium metasilicate, ptfe emulsion for use.Forming the aperture by molten silk or hot-press method is the three dimensional network matrix of 590-74um.
Electrode of the present invention is to prepare by the following method:
A) earlier skeleton, micropore and adhesives are carried out mechanical mixture by above proportioning, reinstall in the mould and press heat demoulding in 2～5 minutes in 100～300 ℃, reenter in the heating furnace in 100～300 ℃ of poromerics that are fired into 590～74 microns, standby as the three dimensional network matrix;
B) by the machinery mode that fills lead or brown lead oxide are mounted in the mesh of three dimensional network matrix, again through drum extrusion, make and inlay particulate and inlay firmly, utilize electroless plating method, make the three dimensional matrix material adhere to conductive layer, inlaying particulate and net matrix bond simultaneously is one;
C) will inlay the net matrix and place oxygen furnace to lead to oxygen treatments applied 15～60 minutes, make the oxidized formation electrochemical layer of inwall of three-dimensional pore space;
D) active matter that makes is coated with carries out on battery grid to be coated with the cream mode, said three-dimensional body places active matter to obtain green plate, with common process green plate is made storage battery pole plate again.
Electrode of the present invention not only is applicable to lead acid accumulator, also is applicable to the non-lead acid accumulator of lithium battery, Ni-MH battery, alkaline Mn cell class.
A large amount of nonmetallic materials (the highest account for active matter volume 90%) of using have constituted of the present invention one big characteristics in the electrode, using nonmetallic materials of the present invention must be very little or insoluble fully to the solubility of acid, simultaneously again can not with any material generation chemical reaction that constitutes active matter.This nonmetallic materials are again to make the material of three-D pore structure easily simultaneously.The selection of material and content depend on design desired mesh size of electrode and capacity requirement.It is another feature of the present invention that active matter is embedded in the three-dimension hole matrix.The size of mesh and the thickness of matrix depend on the physical dimension and the Capacity design of electrode, but the mesh average diameter is between 590-74um.
The present invention has following characteristics and advantage:
1, the invention provides a kind of three dimensional network pore electrod of uniqueness, be applied in the storage battery, nonmetallic materials have promptly been widely applied, compare with the electrode of the lead-acid battery of state-of-the art, it has reduced number of electrodes, has dwindled volume, alleviate weight, thereby improved the specific power and the specific energy of storage battery.
2, another advantage of electrode of the present invention is that electrochemical active material is embedded in the matrix of three-dimension hole, constitute an integral body between matrix and the active material, machinery and electrical property continuity are better, make the resistance loss between active material and the plumbous surface reduce to minimum, the lead-acid battery of kind electrode of packing into is compared with the lead-acid battery of routine, presents very high discharge rate and quick charge capability.
3, electrode of the present invention has changed conventional batteries electroactive substance combination, make active material gel one disintegration process become metal and matrix, matrix and matrix, metal and metal composite connecting mode by the single connecting mode of traditional metal and metal, can prevent effectively that active material from softening prematurely, coming off, thus the useful life of the initial capacity of premature loss battery and shortening battery.
4, because the increase of surface area has slowed down PbS04 and increased the duct of stopping up between the active material because of its molal volume, hinder the conduction phenomenon of ion in the hole, thereby improve battery performance.
5, kind electrode has three-D pore structure, big, the three-dimensional characteristics that connect of surface area, and the utilance of active material is improved, and specific energy increases.Abundant hole and enough big surface area make battery carry out electrochemistry when becoming the stream reaction, can guarantee that sufficient acid flows into, and carries out reaction smoothly.
In a word, the invention provides a kind of novel and unique three-diemsnional electrode, it mainly is applicable to storage battery, more be applicable to lead acid accumulator, the hole of this electrode active material is three-dimensional, be that diameter limits within the specific limits, the solid irregular shape, because the surface area ratio of three-dimension hole two dimension pore structure surface area is much bigger, improve 5～30 times than traditional pole plate, therefore the thickness of electrode is compared with traditional electrode and can be relaxed to 2-3 times, thereby reduced the quantity of electrode in the storage battery, resulting battery is more light than conventional lead-acid battery.The battery of making of battery lead plate of the present invention has more excellent characteristic than traditional battery simultaneously.
The concrete technical scheme of the present invention is:
Electrode of the present invention is made up of grid (traditional), three-dimension hole matrix, electro-chemical activity thing (traditional).
The present invention adopts the electrode matrix of the prefabricated three-D pore structure of nonmetal elder generation, referring to following three-dimension hole electrode matrix electromicroscopic photograph, why adopting nonmetallic materials is because compare with metal, with these prefabricated three-D pore structure materials be easy to get, cheap, easy to manufacture.Make the three dimensional matrix material framework material is arranged, as polyethylene, polytetrafluoroethylene, ultra-high molecular weight polyethylene, high density polyethylene 〉=1,500,000 molecular weight, polypropylene, poromerics selects for use zeolite, active carbon, perlite and adhesives as sodium metasilicate, ptfe emulsion.Make and by molten silk, hot pressing or other method the matrix micro-pore diameter to be remained between 590-74um.Add the method for filling by machinery lead or brown lead oxide particulate are mounted in the mesh, reach particulate through drum extrusion again and inlay firmly.Utilize extraordinary batch (-type) electroless plating method, give three dimensional matrix material conductivity, make mesh diameter trend towards a certain diameter range gradually, inlaying particulate and net matrix bond is one.Have the three-diemsnional electrode basis material of conductivity and the active matter that made made are coated with to carry out make three-diemsnional electrode on grid.
Embodiment
Be the three-diemsnional electrode specific embodiment below.
Embodiment one is with polytetrafluoroethylene, zeolite and the sodium metasilicate ratio mechanical mixture in 13:6:1, and the mould of packing into is in 100～300 ℃ of hot pressing demoulding in 2～5 minutes; Go in the heating furnace and be fired into 590-74um poromerics, formation three-diemsnional electrode matrix in 100～300 ℃; By mode of vibration lead is mounted in the three-diemsnional electrode matrix, three dimensional network matrix nonmetallic materials account for 35% of active matter volume, reach particulate through drum extrusion again and inlay firmly.Utilize electroless plating method, make the three dimensional matrix material adhere to conductive layer, particulate is inlayed in 590～74 microns of mesh diameter maintenances and the net matrix bond is an one, makes said three-dimensional body.Said three-dimensional body inserted charge into pure oxygen in the oxygen furnace and handled 15～60 minutes, make the oxidized formation one deck of inwall electrochemical active material of three-dimension hole; The active matter of making is coated with fills on the cell panel to be coated with the cream mode, said three-dimensional body places active matter, obtains green plate; By traditional handicraft green plate is made storage battery pole plate.
Embodiment two is with ultra-high molecular weight polyethylene (2,000,000 molecular weight), zeolite and the sodium metasilicate ratio mechanical mixture in 13:6:1, and the mould of packing into is in 100～300 ℃ of hot pressing demoulding in 2～5 minutes; Go into heating furnace and be fired into 590-74um poromerics, formation three-diemsnional electrode matrix in 100～300 ℃; By the machinery mode that fills lead is mounted in the three-diemsnional electrode matrix, three dimensional network matrix nonmetallic materials account for 42% of active matter volume.Reaching particulate through drum extrusion again inlays firmly.Utilize electroless plating method, make the three dimensional matrix material adhere to conductive layer, particulate is inlayed in 590-74 microns of mesh diameter maintenances and the net matrix bond is an one, makes said three-dimensional body.Said three-dimensional body inserted charge into pure oxygen in the oxygen furnace and handled 15～60 minutes, make the oxidized formation one deck of inwall electrochemical active material of three-dimension hole; The active matter of making is coated with fills on the cell panel to be coated with the cream mode, said three-dimensional body places active matter, obtains green plate; By traditional handicraft green plate is made storage battery pole plate.
Embodiment three is polyethylene, zeolite, active carbon and the ptfe emulsion ratio mechanical mixture in 12:3:3:1, the mould heat pressure demoulding in 2～5 minutes of packing into; Go into heating furnace and be fired into 590-74um poromerics, form the three-diemsnional electrode matrix; By the machinery mode that fills lead is mounted in the three-diemsnional electrode matrix, three dimensional network matrix nonmetallic materials account for 50% of active matter volume.Reaching particulate through drum extrusion again inlays firmly.Following preparation method is with embodiment 1.
Embodiment four is high density polyethylene, zeolite, active carbon and the ptfe emulsion ratio mechanical mixture in 14.4:3:2:0.6, the mould heat pressure demoulding in 2～5 minutes of packing into; Go into heating furnace and be fired into 590-74um poromerics, form the three-diemsnional electrode matrix; By the machinery mode that fills lead is mounted in the three-diemsnional electrode matrix, three dimensional network matrix nonmetallic materials account for 55% of active matter volume.Reaching particulate through drum extrusion again inlays firmly.Following preparation method is with embodiment 1.
Claims (5)
1, three-dimensional pore space electrode for accumulator, comprise grid, three-dimension hole matrix and active matter, the formation that it is characterized in that this electrode pad is 10～90% three dimensional network matrixes that form that account for the active matter volume with the nonmetallic materials addition content, active matter is embedded in the mesh, obtains having the porous electrode matrix of three-dimensional pore space structure.
2, according to the described three-dimensional pore space electrode for accumulator of claim 1, the preferred amounts that the addition content that it is characterized in that described nonmetallic materials accounts for the active matter volume is 20～60%.
3, according to the described three-dimensional pore space electrode for accumulator of claim 1, it is characterized in that described three-dimension hole electrode matrix mainly is made of TPO framework material, poromerics and binding material, the weight ratio of three kinds of materials is 10～20:3～10:1, and the micro-pore diameter of three-dimensional porous electrode matrix is 590～74 microns.
4,, it is characterized in that described framework material selects polyethylene, polytetrafluoroethylene, high density polyethylene (HDPE), polypropylene for use according to the described three-dimensional pore space electrode for accumulator of claim 3; Poromerics is selected zeolite, perlite, active carbon for use; Binding material is selected sodium metasilicate, ptfe emulsion for use.
5, according to the described three-dimensional pore space electrode for accumulator of claim 1～4, it is characterized in that described three-dimensional pore space electrode not only is applicable to lead acid accumulator, also be applicable to the non-lead acid accumulator of lithium battery, Ni-MH battery, alkaline Mn cell class.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101584378A CN101442113A (en) | 2007-11-22 | 2007-11-22 | Three-dimensional pore space electrode for accumulator |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101584378A CN101442113A (en) | 2007-11-22 | 2007-11-22 | Three-dimensional pore space electrode for accumulator |
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| CN101442113A true CN101442113A (en) | 2009-05-27 |
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| CNA2007101584378A Pending CN101442113A (en) | 2007-11-22 | 2007-11-22 | Three-dimensional pore space electrode for accumulator |
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Open date: 20090527 |