CN108199094A - A kind of bipolarity Asymmetric Supercapacitor energy storage device and its bipolar devices - Google Patents
A kind of bipolarity Asymmetric Supercapacitor energy storage device and its bipolar devices Download PDFInfo
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- CN108199094A CN108199094A CN201611126223.8A CN201611126223A CN108199094A CN 108199094 A CN108199094 A CN 108199094A CN 201611126223 A CN201611126223 A CN 201611126223A CN 108199094 A CN108199094 A CN 108199094A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/18—Lead-acid accumulators with bipolar electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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 discloses a kind of bipolar devices for bipolarity Asymmetric Supercapacitor energy storage device, including：Substrate, the substrate are insulation, and including two opposite surfaces；Anode, the anode include leaded active material and on a surfaces of the substrate；Cathode, the cathode are located on another surface of the substrate；The substrate has electrical connection access, so as to form electrical connection between a positive electrode and a negative electrode；It is characterized in that, the cathode includes carbon containing active material.Carbon lead battery technology and bipolar battery technology are successfully combined togather by the present invention, so as to effectively increase performance of the energy storage device when carrying out two-way high-power, high-frequency, part charge and discharge.
Description
Technical field
The invention mainly relates to bipolarity Asymmetric Supercapacitor energy storage device fields, are directed to a kind of for bipolarity
The bipolar devices of Asymmetric Supercapacitor energy storage device.In addition, further relate to a kind of vehicle comprising aforementioned energy storage device or
Naval vessel.
Background technology
Traditional lead-acid battery has been used more than 100 years, according to a kind of its common structure, a lead-acid battery list
Member includes several positive plates for being alternately arranged and several negative plates, by absorption type glass mat between positive/negative plate
(AGM) diaphragm is separated.The AGM membrane surfaces have many holes so that charged ion etc. can be walked therefrom and mistake.Positive and negative anodes
Plate includes grid and active material, and wherein grid primarily serves mechanical support active material and electric action, and is coated on surface
Active substance.The active material of anode plate surface coating can be brown lead oxide, and the active material of cathode plate surface coating can
To be lead sponge.
Due to both sides major defect, traditional lead-acid battery is not appropriate for a variety of rapid growth emerged in large numbers in the recent period
" two-way high-power, high-frequency, part charge and discharge " emerging application.On the one hand, in quick fraction charge and discharge process, lead sponge
Negative electrode active material surface can generate lead sulfate crystallization (also referred to as " salinization phenomenon "), serious curtailment battery life.The opposing party
Face in order to which electric current is drawn, needs to set bus-bar.The grid and bus-bar of lead increase weight, but it is anti-to be not involved in electrochemistry
Should, lead to the practical than 1/3rd of energy (Wh/Kg) less than theoretical boundary of lead-acid battery.
For many years, the defects of technical staff is designed a lot of ways to improve lead-acid battery.Chinese patent ZL02812335.2
It is exactly one example of which.The asymmetric of lead-acid battery anode and carbon supercapacitor cathode is used which disclose a kind of
Ultracapacitor Energy Storage (also known as " carbon lead battery ").Wherein, cathode is protected by the carbon of copper current collector, conduction/anti-corrosion/waterproof
Layer and the anode active material layer combination composition including activated carbon.Carbon lead battery realizes lead-acid battery and carbon supercapacitor
The two has complementary advantages, so as to longer cycle life, higher ratio energy and specific power, quick fraction charge and discharge, low temperature
Performance is good, safe, full recycling, it is at low cost, cost-effective the advantages that.
Chinese patent ZL200780047314.5 discloses a kind of cathode for above-mentioned lead carbon battery.Five layers of negative polarity node
Structure is lived including the carbon containing cathode except the corrosion resistant/waterproof/conductive protecting layer and protective layer except copper current collector, copper current collector
Property material layer.Due to the presence of corrosion resistant/waterproof/conductive protecting layer, copper current collector does not contact sulfuric acid electrolyte completely, thus from
Corroded by dilute sulfuric acid.Specifically, which includes the expanded graphite film impregnated with paraffin or rosin, paraffin or pine
Perfume is for being fully sealed the hole of graphite flake, so that carbon protective layer is also equipped with water-proof function in addition to conductive and anti-corrosion, protects
Copper current collector is protected not by sulfuric acid corrosion.
Chinese patent ZL201080004102.0 discloses another improvement to traditional lead acid batteries, i.e. bipolarity electricity
Pond does not change in terms of electrochemical principle, but has made innovation to the physical arrangement of lead-acid battery product, reaches improvement
Performance, the double excellent effects for reducing cost.In this scenario, Cell Bipolar component includes an insulating substrate, and both sides are set respectively
The anode and cathode of battery component are equipped with, is provided with multiple holes on an insulating substrate, hole includes conductive solder, by battery component
The anode and cathode of substrate both sides are welded by conductive solder and are connected.When multiple battery components are connected in a manner of continuously arranging
When together, the anode of a component is oppositely arranged with the cathode of another component, and absorption type glass is provided between anode and cathode
Glass fibrofelt (AGM) diaphragm adsorbs dilute sulfuric acid electrolyte on diaphragm.At the both ends of multiple battery components of series connection, pass through terminal
The positive and negative anodes of battery are drawn.In bipolar battery, electric current threading and mistake from the bipolar plates of each battery component so that electricity
Flow path significantly shortens, so as to significantly reduce battery internal resistance.The bipolar lead acid battery is in unit capacity (thousand simultaneously
Watt-hour) under than the lead dosage of traditional monopole lead-acid battery reduce 1/3rd, improve a quarter than energy, specific power adds
Times, cycle life doubles, and totle drilling cost significantly reduces.
The part that above-mentioned several patents are all cited as this patent herein.
Since above-mentioned carbon lead battery and bipolar battery can effectively improve battery in " two-way high-power, high-frequency, portion
Performance during point charge and discharge " improves the ratio energy and specific power of battery, extends cycle life, reduces cost, therefore people
It wants to above two scheme being combined together, creates bipolarity carbon lead battery, have complementary advantages, improve the sexual valence of product
Than.It is not easy to realize however, this is combined.Firstly, because cathode carbon activity texture material is loose, itself cannot directly be welded
It connects, effective be electrically connected can not be formed with anode on the substrate of bipolar battery.Secondly, Chinese patent
Anti-corrosion electric conducting coating disclosed in ZL200780047314.5 carrys out the hole on sealed graphite film using paraffin or rosin, but
The fusing point of paraffin or rosin is at 100 DEG C hereinafter, can not bear bipolar battery anode and cathode passing through the conduction in substrate hole
Solder connection together when required 180 DEG C or so of high temperature, there is serious technical conflict, it is therefore necessary to seek to solve the conflict
Scheme.Otherwise, if paraffin or rosin fusing, will bring both sides risk：1. paraffin or rosin are insulating materials, fusing
Paraffin or rosin afterwards influences the excellent electric contact of protective layer and Carbon anode active material border, leads to the internal resistance of battery to increase；
2. the seal failure part of paraffin or rosin in protective layer, no longer waterproof, acid solution can penetrate protective layer, contact and corrode copper afflux
Body, the copper sulphate for reacting generation are dissolved in water, pollute electrolyte, eventually lead to battery performance and service life big drop.
Due to the above problems, those skilled in the art are difficult to carbon lead battery of the prior art and bipolarity electricity
Pool technology simple superposition combines, and realizes bipolarity Asymmetric Supercapacitor energy storage device (also known as " bipolarity carbon lead battery ").
Invention content
Carbon lead battery technology and bipolar battery technology are effectively bonded together by the present invention, realize bipolarity carbon lead
Battery.The present invention can further improve ratio energy (Wh/Kg), specific power (W/Kg) and the cycle life of carbon lead battery, and energy
It is enough to reduce manufacture cost (), therefore with high cost performance.
According to an aspect of the present invention, it proposes a kind of for the double of bipolarity Asymmetric Supercapacitor energy storage device
Polar components, including：Substrate, the substrate are insulation, and including two opposite surfaces；Anode, the anode include
Leaded positive electrode active materials and on a surface of the substrate；Cathode, the cathode are located at the another of the substrate
On one surface；The substrate has electrical connection access, so as to form electrical connection between a positive electrode and a negative electrode；It is also, described negative
Pole includes carbon containing negative electrode active material.By this scheme, aforementioned carbon lead battery technology and bipolar battery technology can have
It is combined together to effect, further improves carbon lead battery technology and bipolar battery technology in two-way high-power, high-frequency, part
Cost performance under charge and discharge application scenarios.
Wherein, the cathode can include the articulamentum, protective layer, carbon containing activity that are set gradually outward by the substrate
Material layer.Here, " outside " refers to be directed away from the direction of substrate.Since carbon activity texture material is loose, itself cannot be direct
It is welded, therefore is electrically connected carbon containing active material layer with anode there is provided articulamentum.Meanwhile for the company of protection
Corrosion of the layer from acid is connect, conductive corrosion protective covering is provided between articulamentum and carbon containing active material layer, though it is sour in this way
Carbon containing active material layer can be so penetrated, but meeting protected seam separates, and will not corrode articulamentum.
Here the articulamentum can include conductivity and be more than 1.0*105The metal material of Siemens/rice is nonmetallic
Material, such as superconduction carbon fiber, graphene.The articulamentum is preferably sheet metal, and sheet metal is not only good conduction
Body, and can directly implement welding operation.In this way, the articulamentum of cathode easily can be penetrated by substrate by welding
It is reliably electrically connected with anode realization.Meanwhile articulamentum can also play the role of confluence.
Particularly, the sheet metal can include lead or metal.Compared with other metal materials such as copper, although lead
Electric conductivity is weaker, but has other advantages for being difficult to be substituted.On the one hand, lead is in liberal supply, cheap, is very suitable for
In industrialized production, recyclable recycling；On the other hand, lead and sulfuric acid reaction can generate lead sulfate, and lead sulfate indissoluble
Yu Shui so as to form one layer of protective film on the surface of lead, prevents sulfuric acid from further being reacted with lead.Previous, people are simultaneously
This reaction is not intended to occur, it is low to be primarily due to lead sulfate conductivity, can increase battery internal resistance once being formed, influence to have
The electrical connection of effect.But in the present invention, due to the presence of electrical connection access (can also include lead) itself, it can be ensured that anode
Reliable electrical connection between cathode articulamentum.Even if unprotect layer between cathode articulamentum and substrate, there are gaps so that sulphur
Acid penetrates into generate lead sulfate on surface of the articulamentum towards anode, will not increase internal resistance, influence electrical connection.Cause
This, when using lead material do articulamentum when, between articulamentum and substrate blow-by will not cause bad shadow to the implementation of scheme
It rings, the complexity of processing, the cooperation of articulamentum and substrate can be significantly decreased in this way, quality is improved, reduce production cost.Again
On the one hand, if there are flaws for the protective layer of another side so that a little sulfuric acid oozed protective layer, contacted leaded articulamentum,
Reaction, which forms lead sulfate, can equally prevent further corroding for articulamentum.And if articulamentum uses copper, due to reaction generation
Copper sulphate is soluble easily in water, can pollute sulfuric acid electrolyte, and copper gradually can constantly be corroded in long-time use, eventually result in
The energy storage device fails.
Further, the articulamentum can be including three layers, the first layer contacted with substrate and the third layer far from substrate
Including lead (including metal), the second layer between the first layer and the third layer includes at least copper, aluminium and silver
In one kind (including alloy).The articulamentum of above-mentioned three-decker fully meets coating machine to the requirements of base material (for example, anti-
Tension), therefore can protective layer be implemented by ripe electrode coating process, so as to which processing efficiency is able to be promoted, be produced into
Originally it is minimized.Again because the conductivity of the copper, aluminium or silver in the second layer is apparently higher than lead, the electric conductivity of articulamentum is again to carry
It rises, the internal resistance of battery is reduced.Protective layer is implemented, and the protective layer need not do waterproof by ripe electrode coating process
Encapsulation process, such technique greatly simplify product subsequent technique, are produced into so as to greatly improve processing efficiency and reduce
This.Preferably, the first layer and the third layer are formed in by way of plating on the second layer.
In one embodiment, at least part of the protective layer includes graphene.Graphene has excellent conduction
Property and thermal conductivity, and its chemical property is highly stable, therefore is highly suitable as protective layer use.
And in another embodiment, at least part of the protective layer is formed by dry conductive carbon paste.Conductive carbon
Slurry can add in binding agent, special additive in specific proportions by least one of graphite, carbon black, carbon nanotube and carbon fiber
And deionized water is sufficiently stirred and is made.In prior art ZL200780047314.5, disclosed anti-corrosion electric conducting coating makes
With paraffin or rosin come the hole of sealed graphite thin slice, realization water-proof function, so as to avoid internal copper current collector by sulfuric acid corruption
Erosion.But as it was noted above, since the fusing point of paraffin or rosin is relatively low, meeting of being heated in the process subsequently such as welding or use
Fusing, not only influences protecting effect, but also may increase resistance so as to influence to be electrically connected effect, and its processing cost can be very
Height is not easy to automate, quality control difficulties.But in the present embodiment, since articulamentum includes lead, itself just have acidproof
Property, the resistance that the problem of worrying becomes between articulamentum and active material layer may increase with the generation of lead sulfate
Greatly, so as to influence to be electrically connected effect.However, although conductive carbon paste, which has been done, there are many holes on the protective layer of later formation, only lead
Electric corrosion resistant is simultaneously non-watertight, but still suffers from most of area and done by conductive carbon paste occupied by later solid constituent.This portion
Facet product can cover the leaded connection layer segment contacted, prevent sulfuric acid from reacting with it, and ensure that circuit connects.
Further, it after conductive carbon paste has been done and is compressed the part that dry conductive carbon paste is formed so that protect
Sheath internal structure is even closer, and hole substantially reduces so that it is more preferable, more stable with being electrically connected for articulamentum.In addition to this,
Compression also is able to reduce the thickness of the bipolar devices, and more pairs can be accommodated hence for the energy storage device of given thickness
Polar components, so as to improve energy density.Preferably, through overcompression, the thickness of carbon protective layer will reduce 5-45%.
In addition, another protective layer can also be included between the articulamentum and the substrate.Although as it was noted above,
Articulamentum include lead in the case of, due to be electrically connected access presence, it can be ensured that between anode and cathode articulamentum can
By electrical connection, but this conclusion is not particularly suited for the articulamentum of other materials.Increased layer protective layer can be protected other
The articulamentum of material by sulfuric acid corrosion, does not make have moderately good electrical connection between cathode articulamentum and anode, and then prevent from storing up
Energy device internal resistance is increased, reduced performance.
Preferably, the electrical connection access includes the hole formed on the substrate and the conductive solder material in the hole
Material.In this way, the plus plate current-collecting body and cathode articulamentum of substrate both sides realize reliable electrical connection, simple in structure, performance by welding
It is good, at low cost.Also, the fusing point of conductive bonding material is less than substrate fusing point, conductive when occurring thermal runaway inside energy storage device
Welding material is dissolved prior to substrate, is cut off the electrical connection between the positive and negative anodes of bipolar devices, is played the role of internal fuse.
Optionally, the leaded positive electrode active materials include brown lead oxide and/or lead sulfate.
Optionally, it is flat to 4000 in 200 meters squared per grams to include BET specific surface area value for the carbon containing negative electrode active material
The activated carbon in square rice/gram section.
Optionally, the plus plate current-collecting body and individual layer cathode articulamentum include the pure lead thin slice of more than 99.9% degree of purity.
Optionally, described three layers of composite joint layer of cathode include copper foil core layer and cover the degree of purity on core layer two sides
More than 99.9% pure plating lead layer.
Optionally, the solder is included by weight stanniferous 60%, the SnPb63 of lead 40%, 183 degrees Celsius of fusing point.
According to another aspect of the present invention, it is proposed that a kind of bipolarity Asymmetric Supercapacitor energy storage device, including：
Diaphragm and electrolyte and several bipolar devices as previously described, these components are arranged in series as a bipolarity group
For the cathode of part towards the anode of another bipolar devices, the diaphragm and the electrolyte are set to each two neighboring bipolar
Between component.Wherein, the diaphragm can be absorption type glass mat (AGM) diaphragm.The electrolyte can be concentration
27%~38% dilute sulfuric acid aqueous solution.
Preferably, several described bipolar devices of series connection include positive and negative end, are set respectively on the positive and negative end
Anode monopole and cathode monopole are equipped with, the anode single-stage and the cathode single-stage can respectively include the bipolar devices
Positive or negative pole.
According to another aspect of the present invention, it is proposed that a kind of vehicle or naval vessel, it is non-comprising bipolarity as previously described
Symmetrical Ultracapacitor Energy Storage.
Description of the drawings
By reading the detailed description made to non-limiting example made with reference to the following drawings, of the invention is other
Feature, objects and advantages will become more apparent upon：
Fig. 1 is a kind of bipolar devices for bipolarity Asymmetric Supercapacitor energy storage device according to the present invention
The sectional view of one embodiment；
Fig. 2 is a kind of bipolar devices for bipolarity Asymmetric Supercapacitor energy storage device according to the present invention
The sectional view of second embodiment；
Fig. 3 is a kind of bipolar devices for bipolarity Asymmetric Supercapacitor energy storage device according to the present invention
The sectional view of third embodiment, compared with second embodiment, the more layer protective layers of the embodiment；
Fig. 4 is a kind of bipolar devices for bipolarity Asymmetric Supercapacitor energy storage device according to the present invention
The sectional view of 4th embodiment；
Fig. 5 is the section view according to a kind of one embodiment of bipolarity Asymmetric Supercapacitor energy storage device of the present invention
Figure；
Fig. 6 A are according to a kind of vehicle of the present invention, and it is asymmetric super which includes a kind of bipolarity according to the present invention
Energy-storing device with capacitor.
Fig. 6 B are according to a kind of naval vessel of the present invention, and it is asymmetric super which includes a kind of bipolarity according to the present invention
Energy-storing device with capacitor.
Specific embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the present invention is described in further detail.It should be appreciated that herein
Described embodiment is merely to illustrate and explain the present invention, and is not intended to limit the present invention.Based on the embodiments of the present invention,
The other embodiment that those of ordinary skill in the art are obtained in the case where not making the creative labor, belongs to the present invention
The range of protection.
Fig. 1 shows a kind of bipolarity group for bipolarity Asymmetric Supercapacitor energy storage device according to the present invention
The sectional view of one embodiment of part.It can be seen from the figure that the bipolar devices include substrate 18, anode 11, cathode 10.
Wherein, substrate 18 be insulation, and including on the contrary two surfaces 16,17, respectively with anode 11 and cathode 10
Contact.Substrate 18 and 10 cooperating of anode 11 and cathode, are able to carry out following one or more functions：(1) as battery
Unit separates, and prevents the electrolyte between adjacent cell, and (2) effectively support the other parts of bipolar devices,
(3) effective sealing is cooperatively formed with the other component of bipolarity Asymmetric Supercapacitor energy storage device.Substrate 18 by with
There is the material of high chemical stability and electrochemical stability to form in electrolyte (for example, sulfuric acid solution) contact, so that
Substrate 18 will not be with being corroded during electrolyte contacts, the electrochemical reaction being not involved in battery unit.Preferably, substrate 18
Fusing point is higher than the fusing point of other any conductive materials in bipolarity Asymmetric Supercapacitor energy storage device construction.Substrate 18 can be by
Polymer material is formed, including but not limited to thermoplastic, thermosetting plastics, include the material of elastomer or its any group
It closes.The example of workable polymer material includes polyamide (PA), polypropylene (PP), polyester (PET, PBT), acrylonitrile fourth two
Alkene styrene polymer (ABS), makrolon (Polycarbonate, PC), polyformaldehyde (Polyacetal, Polyoxy
Methylene, POM), polyphenylene oxide (Polyphenylene Oxide, PPO), polyphenylene sulfide (Polyphenylene
Sulfide, PPS) or any combination of them.
Anode 11 includes leaded active material 9 and plus plate current-collecting body 8, and leaded active material 9 is coated in anode collection
On body 8.Plus plate current-collecting body 8 is located on a surface 16 of substrate 18.Preferably, leaded active material 9 can be
Lead sulfate and/or brown lead oxide, plus plate current-collecting body 8 can be lead foils.Preferably, plus plate current-collecting body 8 for degree of purity 99.9% with
On pure lead thin slice.
Cathode 10 includes carbon containing active material 7 and cathode gratings 6, and carbon containing active material 7 is coated in cathode gratings 6
On.Cathode gratings 6 is located on another surface 17 of substrate 18.The carbon containing active material 7 can be any predominantly carbon-based
Material.In specific embodiment, carbon containing active material 7 can be carbon black, activated carbon etc..Cathode gratings 6 can be by
Any metal or alloy is formed.
In order to realize the electrical connection between anode 11 and cathode 10, there is electrical connection access 15 on substrate 18.In the present invention
Electrical connection access 15 can be accomplished in several ways, the present invention to this without uniquely limiting.As a preferred embodiment,
The hole 151 on substrate 18 and the conductive bonding material 152 in hole 151 can be included by being electrically connected access 15.On substrate 18
Hole 151 can be variously-shaped, such as round, rectangular etc..Hole 151 on substrate 18 can also have multiple.On substrate 18
The shape sum number amount in hole 151 depends on the material of substrate 18, property coated in the active material on anode 11 and cathode 10 etc.
Multiple factors.Conductive bonding material 152 in hole 151 can include in the metals such as lead, tin, nickel, zinc, lithium, antimony, copper, bismuth
At least one.Preferably, conductive bonding material 152 can include the SnPb63 of stanniferous by weight 60%, lead 40%,
Fusing point is 183 degrees Celsius.It should be understood that conductive bonding material 152 is known to those skilled in the art.It is preferred that
Ground, the fusing point of conductive bonding material 152 is less than the fusing point of substrate 18, inside bipolarity Asymmetric Supercapacitor energy storage device
When there is thermal runaway, conductive bonding material 152 is melted prior to substrate 18, and the electrical connection between the positive and negative anodes of bipolar devices is therewith
It interrupts.Here, conductive bonding material 152 plays the role of internal fuse.
Further, the conductive bonding material 152 in hole 151 is by the plus plate current-collecting body 8 of anode 11 and cathode 10
Cathode gratings 6 connects, it is achieved thereby that the electrical connection between anode 11 and cathode 10.
Through the above technical solutions, lead carbon battery technology and bipolar battery technology are combined togather, so as to effectively carry
High performance of the energy storage device when carrying out two-way high-power, high-frequency, part charge and discharge, solves those skilled in the art very
The technical issues of thirsting for solving for a long time.
Fig. 2 shows the of a kind of bipolar devices for bipolarity Asymmetric Supercapacitor energy storage device of the invention
The sectional view of two embodiments.Unlike bipolar devices in Fig. 1, the cathode of the bipolar devices includes three-decker.
Specifically, cathode can include the articulamentum 12, protective layer 13, the carbon containing active material layer that are set gradually outward by substrate 18
14.Here, " outside " refers to be directed away from the direction of substrate 18.Carbon containing active material quality is loose, in industrial practice, very
Hardly possible directly welds it, therefore for easy to operate, reduction production cost, will there is provided articulamentum 12 in this programme
Carbon containing active material layer 14 is electrically connected with anode.Meanwhile in order to protect articulamentum 12 from the corrosion of acid, in articulamentum
There is provided protective layers 13 again between 12 and carbon containing active material layer 14.Protective layer 13 is conductive, acidproof, and acid allows in this way
Carbon containing active material layer 14 is crossed, but meeting protected seam 13 separates, so as to which effective protection articulamentum 12 is not by acid attack.
Articulamentum 12 can include sheet metal.Metal is not only good electric conductor, and can directly implement to weld
Operation.It is electrically connected, and then realizes just with anode 11 in this way, can articulamentum 12 easily be penetrated substrate 18 by welding
Being electrically connected between pole 11 and carbon containing active material layer 14.
Particularly, sheet metal can include pure lead or metal.Compared with the metal materials such as copper, although the electric conductivity of lead
Can be weaker, but have the advantage for being difficult to be substituted.On the one hand, lead is in liberal supply, cheap, and it is big to be very suitable for industrialization
Production, recyclable recycling.Importantly, on the other hand, lead and sulfuric acid reaction can generate lead sulfate, and lead sulfate indissoluble
Yu Shui so as to form one layer of protective film on the surface of lead, prevents sulfuric acid from further being reacted with lead.Previous, people are simultaneously
This reaction is not intended to occur, it is low to be primarily due to lead sulfate conductivity, can battery internal resistance be increased once being formed, influences
Effective electrical connection.But in the present invention, due to the presence of electrical connection access 15 (can also include lead) itself, it can be ensured that
It is reliably electrically connected between anode 11 and cathode articulamentum 12, even if unprotect layer between cathode articulamentum 12 and substrate 18, exists
Gap so that sulfuric acid penetrates into generate lead sulfate in the remaining surface of articulamentum 12, will not increase internal resistance, influence electricity
Connection.Therefore, when doing articulamentum 12 using lead material, blow-by will not be to the implementation of scheme between articulamentum 12 and substrate 18
Harmful effect is caused, the complexity of processing, the cooperation of articulamentum 12 and substrate 18 can be significantly decreased in this way, improve quality,
Reduce production cost.In another aspect, if there are flaws for protective layer 13 so that a little sulfuric acid oozed protective layer 13, contacted lead
Articulamentum 12, further corroding for articulamentum 12 can equally be prevented by reacting the lead sulfate of generation.And if articulamentum 12 uses copper,
Due to reaction generation copper sulphate it is soluble easily in water, sulfuric acid electrolyte can be polluted, in long-time use copper can gradually constantly by
Corrosion eventually results in energy storage device failure.
In one embodiment, at least part of protective layer 13 includes graphene.Graphene has excellent electric conductivity
And thermal conductivity, and its chemical property is highly stable, therefore is highly suitable as protective layer 13 and uses.
In another embodiment, at least part of protective layer 13 can also be formed by dry conductive carbon paste.It is existing
In technology ZL200780047314.5, disclosed anti-corrosion electric conducting coating comes the hole of sealed graphite thin slice using paraffin or rosin
Gap realizes water-proof function, so as to avoid internal copper current collector by sulfuric acid corrosion.But as it was noted above, due to paraffin or pine
Fragrant fusing point is relatively low, is heated and can melt in the process subsequently such as welding or use, not only influences protecting effect, but also may
Increase resistance so as to influence to be electrically connected effect, and its processing cost can be very high, is not easy to automate, quality control difficulties.But
It is that in the present embodiment, since articulamentum 12 includes lead, itself just has acid resistance, and the problem of worrying becomes articulamentum
Resistance between 12 and carbon containing active material layer 14 may increase with the generation of lead sulfate, so as to influence electrical connection effect
Fruit.However, although conductive carbon paste, which has been done, many holes on the protective layer 13 of later formation, conductive corrosion resistant is simultaneously non-watertight,
It is to still suffer from most of area to have been done by conductive carbon paste occupied by later solid constituent.This area can will be contacted
Leaded 12 part of articulamentum covers, and prevents sulfuric acid from reacting with it, and ensures that circuit connects.Therefore conductive carbon paste shape is used
It is apparent into 13 advantage of protective layer.
Further, by being compressed to protective layer 13 so that the internal structure of protective layer 13 is even closer, and hole is shown
It writes and reduces so that it is more preferable, more stable with being electrically connected for articulamentum 12.In addition to this, compression also is able to reduce the bipolarity
The thickness of component can accommodate more bipolar devices hence for the energy storage device of given thickness, close so as to improve energy
Degree.Preferably, through overcompression, size of the part formed by dry conductive carbon paste on compression direction reduces 5-
45%.
In addition, Fig. 3 shows a kind of bipolarity group for bipolarity Asymmetric Supercapacitor energy storage device of the invention
The sectional view of the third embodiment of part.Unlike second embodiment, further included between articulamentum 12 and substrate 18
Another protective layer 31.Although as it was noted above, in the case where articulamentum 12 includes lead, since electrical connection access 15 is deposited
, it can be ensured that the electrical connection between anode 11 and articulamentum 12, but this conclusion is not particularly suited for the connection of other materials
Layer 12.Increased layer protective layer 31 can protect the articulamentum 12 of other materials to make electrical connection access 15 not by sulfuric acid corrosion
There is moderately good electrical connection between articulamentum 12, and then prevent the internal resistance of bipolarity Asymmetric Supercapacitor energy storage device from increasing
High, reduced performance.The material and structure of second protective layer 31 can be identical with protective layer 13.
Fig. 4 shows the of a kind of bipolar devices for bipolarity Asymmetric Supercapacitor energy storage device of the invention
The sectional view of four embodiments.Unlike bipolar devices in second embodiment, the articulamentum packet of the bipolar devices
Include three-decker.Specifically, the first layer 121 contacted with substrate 18 and the third layer 123 far from substrate 18 include lead (including lead
Alloy), the second layer 122 between first layer 121 and third layer 123 includes at least one of copper, aluminium or silver.
The articulamentum of above-mentioned three-decker fully meets requirements (for example, tension stress) of the coating machine to base material, therefore
Can protective layer 13 be implemented by ripe electrode coating process, so as to which processing efficiency is able to promotion, production cost is dropped
It is low.Again because the conductivity of the copper, aluminium or silver in the second layer 122 is apparently higher than lead, the electric conductivity of articulamentum is again to be promoted, electricity
The internal resistance in pond is reduced.
Preferably, in this embodiment, first layer 121 and third layer 123 are formed in by way of plating
On two layer 122.By ripe wet plating or chemical plating, can in the lead-coat of two surface deposition compacts of the second layer 122,
Its thickness can be from several microns to tens micron, which can effectively protect the second layer 122 not corroded by sulfuric acid.This
Outside, it is electroplated the structure for causing articulamentum is more firm, and the thickness of articulamentum also can be reduced further.
Preferably, in this embodiment, at least part of protective layer 13 includes graphene.Graphene has excellent
Different electric conductivity and thermal conductivity, and its chemical property is highly stable, therefore is highly suitable as protective layer 13 and uses.
Fig. 5 shows a kind of section view of one embodiment of bipolarity Asymmetric Supercapacitor energy storage device of the present invention
Figure.The bipolarity Asymmetric Supercapacitor energy storage device includes：Diaphragm 19 and electrolyte (not drawing) and several as before
Bipolar devices described in text, the cathode that these bipolar devices are arranged in series as a bipolar devices are bipolar towards another
The anode of property component, diaphragm 19 and electrolyte are set between each two neighboring bipolar component.Wherein, the tool of bipolar devices
Body quantity can be determined according to the concrete application demand of bipolarity Asymmetric Supercapacitor energy storage device.Preferably, it goes here and there
Several bipolar devices of connection include positive end and negative end, and anode monopole 20 is respectively arranged on positive end and negative end
With cathode monopole 21, anode single-stage 20 and cathode single-stage 21 can have the knot identical or different with aforementioned positive electrode 11 and cathode 10
Structure, and be connected respectively with positive terminal 23 and negative terminal 24.
For electrolyte, any suitable acidic electrolyte bath can be used.Electrolyte can be liquid or gel form.
Preferably, electrolyte can be the solution for including sulfuric acid.Electrolyte specifically selects can be by those skilled in the art's root
It is determined according to the composition of bipolar devices.Diaphragm 19 is used to maintain appropriate separation distance between adjacent electrode.
Preferably, diaphragm can be absorption type glass mat (AGM) diaphragm, and electrolyte adsorbs thereon.
It should be understood that the bipolarity Asymmetric Supercapacitor energy storage device further comprise babinet, terminal and
The common attribute of other bipolar battery groups.
Fig. 6 A show a kind of vehicle of the present invention, and Fig. 6 B show a kind of naval vessel of the present invention, this vehicle or naval vessel installation
Bipolarity Asymmetric Supercapacitor energy storage device 30 as previously described.Therefore, it is mounted with the asymmetric super electricity of bipolarity
The vehicle or naval vessel of container energy storage device have superior performance when carrying out two-way high-power, high-frequency, part charge and discharge.
It is obvious to a person skilled in the art that the present invention is not limited to the details of above-mentioned exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive.
Claims (15)
1. a kind of bipolar devices for bipolarity Asymmetric Supercapacitor energy storage device, including：
Substrate, the substrate are insulation, and including two opposite surfaces；
Anode, the anode include leaded positive electrode active materials and on a surfaces of the substrate；
Cathode, the cathode are located on another surface of the substrate；
The substrate has electrical connection access, so as to form electrical connection between a positive electrode and a negative electrode；
It is characterized in that, the cathode includes carbon containing negative electrode active material.
2. bipolar devices according to claim 1, which is characterized in that the cathode is included by the substrate outward successively
Articulamentum, protective layer, the carbon containing active material layer of setting.
3. bipolar devices according to claim 2, which is characterized in that the articulamentum includes sheet metal.
4. bipolar devices according to claim 3, which is characterized in that the sheet metal includes lead or metal.
5. bipolar devices according to claim 2, which is characterized in that the articulamentum includes three layers, is contacted with substrate
First layer and third layer far from substrate include lead, the second layer between the first layer and the third layer at least wraps
Include one kind in copper, aluminium and silver.
6. bipolar devices according to claim 5, which is characterized in that the first layer and the third layer pass through plating
Mode be formed on the second layer.
7. according to bipolar devices any one of in claim 2-6, which is characterized in that at least the one of the protective layer
Part includes graphene.
8. according to bipolar devices any one of in claim 4-6, which is characterized in that at least the one of the protective layer
Part is formed by dry conductive carbon paste.
9. bipolar devices according to claim 8, which is characterized in that leading the part that dry conductive carbon paste is formed
After electrical carbon slurry has been done and compressed.
10. according to bipolar devices any one of in claim 1-9, which is characterized in that in the articulamentum and institute
It states and further includes another protective layer between substrate.
11. according to bipolar devices any one of in claim 1-9, which is characterized in that the electrical connection access packet
Include the hole formed on the substrate and the conductive bonding material in the hole.
12. bipolar devices according to claim 9, which is characterized in that through overcompression, formed by dry conductive carbon paste
Size of the part on compression direction reduce 5-45%.
13. a kind of bipolarity Asymmetric Supercapacitor energy storage device, including：
Diaphragm and electrolyte and
Several such as bipolar devices any one of in claim 1-12, these components be arranged in series as one it is bipolar
Property component cathode towards the anode of another bipolar devices, it is adjacent double that the diaphragm and the electrolyte are set to each two
Between polar components.
14. bipolarity Asymmetric Supercapacitor energy storage device according to claim 13, which is characterized in that the institute of series connection
It states several bipolar devices and includes positive and negative end, anode monopole or cathode monopole are respectively arranged on the positive and negative end,
The anode single-stage and the cathode single-stage respectively include the anode and cathode of the bipolar devices.
15. a kind of vehicle or naval vessel, which is characterized in that non-comprising bipolarity any one of in such as claim 13-14
Symmetrical Ultracapacitor Energy Storage.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109637818A (en) * | 2018-12-29 | 2019-04-16 | 苏州大学 | A kind of lead carbon supercapacitor |
| CN111584823A (en) * | 2019-02-19 | 2020-08-25 | 宁德新能源科技有限公司 | Pole piece, battery core and battery |
| TWI786843B (en) * | 2021-09-23 | 2022-12-11 | 百樂電池股份有限公司 | Through-hole bipolar plate structure applied to lead-acid energy storage battery and its lead-acid energy storage battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6316148B1 (en) * | 2000-08-31 | 2001-11-13 | Condord Battery Corporation | Foil-encapsulated, lightweight, high energy electrodes for lead-acid batteries |
| CN2473750Y (en) * | 2001-03-26 | 2002-01-23 | 赵亮 | Lead acid accumulator grating |
| US20060292384A1 (en) * | 2005-06-24 | 2006-12-28 | Universal Supercapacitors Llc | Current collector for double electric layer electrochemical capacitors and method of manufacture thereof |
| CN102272978A (en) * | 2009-01-21 | 2011-12-07 | 高级电池概念有限责任公司 | bipolar battery assembly |
| CN103515579A (en) * | 2012-06-21 | 2014-01-15 | 中国人民解放军63971部队 | Negative plate of lead storage battery |
-
2016
- 2016-12-08 CN CN201611126223.8A patent/CN108199094A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6316148B1 (en) * | 2000-08-31 | 2001-11-13 | Condord Battery Corporation | Foil-encapsulated, lightweight, high energy electrodes for lead-acid batteries |
| CN2473750Y (en) * | 2001-03-26 | 2002-01-23 | 赵亮 | Lead acid accumulator grating |
| US20060292384A1 (en) * | 2005-06-24 | 2006-12-28 | Universal Supercapacitors Llc | Current collector for double electric layer electrochemical capacitors and method of manufacture thereof |
| CN102272978A (en) * | 2009-01-21 | 2011-12-07 | 高级电池概念有限责任公司 | bipolar battery assembly |
| CN103515579A (en) * | 2012-06-21 | 2014-01-15 | 中国人民解放军63971部队 | Negative plate of lead storage battery |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109637818A (en) * | 2018-12-29 | 2019-04-16 | 苏州大学 | A kind of lead carbon supercapacitor |
| CN111584823A (en) * | 2019-02-19 | 2020-08-25 | 宁德新能源科技有限公司 | Pole piece, battery core and battery |
| WO2020168879A1 (en) * | 2019-02-19 | 2020-08-27 | 宁德新能源科技有限公司 | Pole piece, cell and battery |
| CN111584823B (en) * | 2019-02-19 | 2022-01-25 | 宁德新能源科技有限公司 | Pole piece, battery core and battery |
| TWI786843B (en) * | 2021-09-23 | 2022-12-11 | 百樂電池股份有限公司 | Through-hole bipolar plate structure applied to lead-acid energy storage battery and its lead-acid energy storage battery |
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