CN102623756A - Bipolar battery made from thin film composite material and bipolar plate base of bipolar battery - Google Patents
Bipolar battery made from thin film composite material and bipolar plate base of bipolar battery Download PDFInfo
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- CN102623756A CN102623756A CN201210115319XA CN201210115319A CN102623756A CN 102623756 A CN102623756 A CN 102623756A CN 201210115319X A CN201210115319X A CN 201210115319XA CN 201210115319 A CN201210115319 A CN 201210115319A CN 102623756 A CN102623756 A CN 102623756A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to the technical field of batteries, in particular to a bipolar battery made from a thin film composite material and a bipolar plate base of the bipolar battery. The bipolar battery comprises the base and one or more conductive particles arranged in the base, wherein the base is made from a thermoset or thermoplastic high-molecule polymer; the conductive particles are uniformly distributed in the base; the diameter of each conductive particle is greater than the thickness of the base; and the conductive particles are protruded from the upper surface and the lower surface of the base. According to the bipolar battery made from the thin film composite material and the bipolar plate base of the bipolar battery, the thermoset or thermoplastic high-molecule polymer is adopted, and the conductive particles are embedded into the bipolar substrate, so that a high-performance storage battery can be prepared; and furthermore, under the condition of 80 percent of discharge, the battery can be used for more than 1,000 times, so that the technical shortcomings in the prior art are overcome, and multiple technical barriers are solved. The prepared bipolar thin film composite material battery has the advantages of high corrosion resistance, light weight, low cost and the like and can meet the condition of large-scale manufacturing.
Description
Technical field
The present invention relates to a kind of battery, relate in particular to a kind of film composite material bipolar cell and bipolar plates matrix thereof.
Background technology
Battery is divided into primary cell and secondary cell, and wherein secondary cell refers to the battery of charge and discharge repeatedly.And in the secondary cell the earliest, most widely used be lead acid accumulator, it can use one pole or bipolar design, and the accurate bipolar design of single bipolar mutual use is also arranged.
In traditional one pole battery, the electric current that active material produced is sent to collector and arrives next batteries through interconnective lug.And bipolar cell is superior more a lot of in electric power output than traditional one pole battery; Be applied to the two sides of bipolar substrate because of its active material; Electric current can flow to next batteries from substrate; Current path is extremely short, so the loss of charge that in circuit, causes because of ohmic drop has reached minimum, therefore the battery volume also significantly reduces.
In bipolar lead-acid battery, the effect of substrate is vital.Substrate not only connects internal cell but also hold active material, and keeps apart each baby battery.Substrate must keep its conductivity under the plumbic acid corrosive environment, and blocking-up adjacent cell electrolyte is communicated with, and must not participate in cell reaction or the loop is provided for self-discharge of battery.These just require substrate must be conductivity to be arranged, be insoluble to sulfuric acid, in the electrochemical window of battery, keep stable and have higher hydrogen-oxygen overpotential ability, does not participate in cell reaction, and cell active materials is had the good adsorption ability, also will be easy to processing and sealing.
Therefore, as bipolar battery, it is what time following nothing more than to need the technical problem that will solve badly:
(1) sealing problem between the adjacent monomer battery;
(2) power loss that causes owing to contact resistance;
The corrosion of the bipolar plates that (3) causes owing to electrolyte;
Whether (4) complexity of manufacture craft helps large-scale production.
At present, to above problem, all there are some patent or technology about the preparation of bipolar battery matrix in each state.These patents or technology or do not elaborate, even idea just; There is not feasibility on the technology; Perhaps feasible, but because reasons such as cost can't realize commercialization.Such as:
China's CN200410014945.5 patent has been described on plastic plate, to wear and has been compiled lead-sheathing and mould core compound wire or lead coated carbon fibre core compound wire and replace titanium plate or the corrosion resistant plate conduction central layer as bipolar plates.On the one hand, this method adopts the preparation of compound wire complicated, and it is very low that cost may not be certain; On the other hand, when the pole plate area is big, the perforation coiling will become less feasible.
The U.S. 4,658, No. 499 patent has been described a kind of a kind of bipolar cell substrate that in the hole of thermoplastic resin, adds conductive particle.Particle can become cylindrical shape and fusion under hot pressing.Because substrate has used thermoplastic resin, must before putting into particle, carry out hole, and the necessary hot melt part of thermoplastic resin is with the sealing particle.But the plastics behind the hot melt can make the frosting of immobilized particles long-pending not enough again.This can cause the liquid infiltration to pass substrate conversely again, thereby damages battery.
In addition, in the prior art, have and use the early stage bipolarity lead-acid battery of stereotype as substrate.Active material is attached on the substrate, and stereotype is deposited between the U-shaped rubber washer.This plumbic acid bipolar cell exists and is difficult for the problem that sealing, substrate are easy to corrode and ability is low; Also have design to adopt the viscose glue conduct electricity to be bonded at the titanium plate on the stereotype, titanium through regular meeting's passivation, and in order to protect titanium, generally can add the golden or plumbous coating of last layer in lead-acid battery, and this also can increase the weight and the cost of battery; In other designs; Use gold-plated titanium plate or conductive plastics to be used as substrate in addition; The former is abandoned because of the difficulty of making atresia coated plate and the availability aspect that keeps titanium; And attempt adds in the conductive epoxy derivative that can extensively obtain as the way of conductive fillers such as carbon, graphite, copper or silver because of all failing with the reaction of battery context; And that the carbon dust that adds glass-like is used as the trial of epoxy resin filler is very successful in beginning, but because the anodal interfacial corrosion of substrate, it is all not too successful to be coated with changing into of cream and active material.
Therefore, just need a kind of new bipolar lead-acid battery technology and can overcome above-mentioned all difficulties.
Summary of the invention
The present invention provides a kind of film composite material bipolar cell and bipolar plates matrix thereof in order to solve the problem that exists in the prior art.
In order to overcome the defective that exists in the background technology, the technical solution adopted for the present invention to solve the technical problems is: this film composite material bipolar cell and bipolar plates matrix thereof comprise matrix; The conductive particle that places matrix to be provided with; Said matrix is processed by thermosetting or thermoplastic polyester, and said conductive particle places the matrix latticed form to distribute, and is provided with one or more conductive particles; The diameter of said conductive particle is greater than the thickness of matrix; And protrude in the upper and lower surfaces of matrix, and said matrix two sides is covered with conductive metal film, and said conductive metal film contacts with the conductive particle conduction of giving prominence at matrix surface; Conductive metal film obtains required bipolar sheets through precompressed, hot pressing, cooling, the demoulding, is assembled into two and batteries after bipolar sheets is coated with cream.
According to another embodiment of the invention, further comprise after said conductive metal film is through surface treatment overlay film again, that said surface treatment comprises is inorganic, organic acid chemical treatment or polishing, polishing physical treatment; Conductive metal film covers on substrate and obtains required bipolar sheets through precompressed, hot pressing, cooling and the demoulding, and said precompressed, hot pressing, cooling and the demoulding are all carried out in mould, and described hot pressing time is 1 to 20min; Pressure is 0.1 to 20MPa; Temperature is that the type of cooling comprises natural cooling and water-cooled between 130 to 280 ℃, cooling time at 10s between the 30min; During the said demoulding in mould spraying help material; Comprise general oiliness, neutrality, dryness release agent, or carry out wax spray, spray demoulding silica gel, or plating mold release film material.
According to another embodiment of the invention; Comprise that further the described cream that is coated with is to smear negative electrode active material and positive active material on the conductive metal film that covers on pressing and forming bipolar sheets two sides; Said bipolar sheets places interior each bipolar sheets of the outer box of battery to be separated by barrier film and contiguous bipolar sheets; The bipolar cell both sides of being made up of bipolar sheets are anodal one pole sheet and negative pole one pole sheet; Apply positive active material or negative electrode active material on said anodal one pole sheet or the negative pole one pole sheet, the outer box both sides of battery are provided with that positive pole is drawn pole and negative pole is drawn pole.
According to another embodiment of the invention, comprise that further said thermosetting or thermoplastic polymer comprise one or more the combination in polyethylene, polypropylene, polybutadiene, polyphenyl dioctyl phthalate glycol ester and ABS powder and the section bar thereof etc.
According to another embodiment of the invention, comprise that further said matrix thickness is between 0.1 to 2mm.
According to another embodiment of the invention, comprise that further said conductive particle processed by conducting metal and conductive non-metals material, said conducting metal is lead material or glassy metal, and said conductive non-metals is a material with carbon element.
According to another embodiment of the invention, the volume ratio that further comprises said conductive particle and matrix is between 0.1% to 10%.
According to another embodiment of the invention, the size that further comprises said conductive particle at 0.13mm between the 2.5mm.
According to another embodiment of the invention, comprise that further distance between the said conductive particle is between 0.5 to 20mm.
According to another embodiment of the invention, the dot matrix that further the comprises said conductive particle side can be employed in matrix that distributes distributes, and both sides distribute simultaneously, and method such as two side portions distribution is carried out.
The invention has the beneficial effects as follows: this film composite material bipolar cell and bipolar plates matrix adopting thermosetting thereof or thermoplastic polyester and on bipolar substrate, embed conductive particle; Can produce a kind of high-energy battery; And the following life-span of deep discharge 80% is long above 1000 times; Still can keep the high-energy lead-acid battery of initial capacity more than 85%, overcome the technological deficiency of current existence, and; The prepared bipolar film composite material lead-acid battery of the present invention has advantages such as corrosion resistant performance is good, in light weight, with low cost, and satisfies the extensive condition of making.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
Fig. 1 is the lattice structure sketch map of bipolar cell substrate of the present invention;
Fig. 2 is the structure of film sketch map of bipolar cell substrate of the present invention;
Fig. 3 is bipolar cell of the present invention and package assembly sketch map thereof;
Wherein: 1, matrix, 2, conductive particle, 3, conductive metal film, 4, negative electrode active material, 5, positive active material, 6, barrier film, 7, anodal one pole sheet, 8, negative pole one pole sheet, 9, positive pole draws pole, 10, negative pole draws pole, 11, the outer box of battery.
Embodiment
Fig. 1 is the lattice structure sketch map of bipolar cell substrate of the present invention; Comprise matrix 1 among the figure, the conductive particle 2 that places matrix 1 to be provided with, matrix 1 is processed by thermosetting or thermoplastic polyester; Conductive particle 2 places matrix 1 latticed form to distribute; Be provided with one or more conductive particles 2, the diameter of conductive particle 2 is thicker slightly than the thickness of matrix 1, and protrudes in the upper and lower surfaces of matrix 1.
In Fig. 1, matrix 1 is processed such as polyethylene, polypropylene, polybutadiene or polyphenyl dioctyl phthalate glycol ester materials such as (PET) by acidproof thermosetting or thermoplastic polyester.Conductive particle 2 is spaced from each other several millimeters to several centimetres distance, and specifically the size by conductivity and particle decides.The diameter R of conductive particle 2 approximately is the 110%-140% of matrix 1 thickness d.Conductive particle 2 can be any material that is suitable for conducting electricity, like lead, amorphous carbon or amorphous metal.These materials and numerical value just illustrate, and specifically can and should according to circumstances select, and what this example adopted is amorphous state metallic lead ball.
Thermosetting or thermoplastic polyester comprise one or more the combination in polyethylene, polypropylene, polybutadiene, polyphenyl dioctyl phthalate glycol ester and ABS powder and the section bar thereof etc.This material can produce the high-energy lead-acid battery more than 85% that still can keep initial capacity after the deep discharge circulation that a kind of life-span reaches 600 times 80%.
Conductive particle 2 is processed by conducting metal and conductive non-metals material, and said conducting metal is lead material or glassy metal, and said conductive non-metals is a material with carbon element.
The volume ratio of conductive particle 2 and matrix 1 is between 0.1% to 10%.Preferably between 0.5% to 1%.
The size of conductive particle 2 at 0.13mm between the 2.5mm.Preferably at 0.3mm between the 2mm.
Distance between the conductive particle 2 is between 0.5 to 20mm.Optimum distance is 1 to 10mm.
The dot matrix of conductive particle 2 side that can be employed in matrix that distributes distributes, and both sides distribute simultaneously, and method such as two side portions distribution is carried out.
Fig. 2 is the structure of film sketch map of bipolar cell substrate of the present invention; Matrix 1 two sides is covered with conductive metal film 3; Conductive metal film 3 contacts with conductive particle 2 conductions of giving prominence on matrix 1 surface; Conductive metal film 3 obtains required bipolar sheets through precompressed, hot pressing, cooling, the demoulding, is assembled into two and batteries after bipolar sheets is coated with cream.Conductive metal film 3 is through overlay film again after the surface treatment, and that said surface treatment comprises is inorganic, organic acid chemical treatment or polishing, polishing physical treatment, and conductive metal film 3 covers on substrate 1 and obtains required bipolar sheets through precompressed, hot pressing, cooling and the demoulding; Said precompressed, hot pressing, cooling and the demoulding are all carried out in mould, and described hot pressing time is 1 to 20min, and pressure is 0.1 to 20MPa; Temperature is between 130 to 280 ℃; The type of cooling comprises natural cooling and water-cooled, cooling time at 10s between the 30min, during the said demoulding in mould spraying help material; Comprise general oiliness, neutrality, dryness release agent; Or carry out wax spray, spray demoulding silica gel, or plating mold release film material, carry out the demoulding then.
In Fig. 2, there is matrix 1 surface of conductive particle 2 to handle in dot matrix, surface treatment comprises acid treatment, glue processing and sanding and polishing or the like, is covered with conductive metal film 3 after the processing again.What adopt in the present embodiment is the metal lead foil.50 microns of conductive metal film 3 thickness on matrix 1 both sides, the thickness of matrix 1 is about 800 microns.After covering conductive metal film 3, place precompressed machinery to carry out precompressed above-mentioned base material, squeeze time 20min, pressure 2MPa, the precompressed temperature is 150 ℃; After the precompressed it is carried out hot pressing, hot pressing is controlled at 250 ℃, and 15MPa, hot pressing time are controlled at the 15min moulding; Subsequently with its cool off, the demoulding obtains required film composite material bipolar sheets.Above operating parameter specifically can and should according to circumstances be selected.
Process the used film matrix of bipolar cell through dot matrix, overlay film, precompressed, hot pressing, cold and detached, the demoulding.Particularly, be to be base material with the high molecule plastic, conducting metal or conductive non-metals particle are embedded body, and it at suitable pressure and temperature compacted under, is made required bipolar electrode.Then, with this bipolar plates matrix assembling preparation high energy bipolar cell.
Be characterized in comprising following process:
(1) dot matrix: conductive particle is evenly distributed on the plastic basis material;
(2) overlay film: the substrate surface treatment with above-mentioned embedding conductive particle is covered with metallic film;
(3) precompressed: the base material of above-mentioned overlay film is put into the just precompressed of precompressed machinery;
(4) hot pressing: with above-mentioned just hot pressing of tectorial backing material, moulding through precompressed;
(5) cold mould: above-mentioned hot-forming bipolar sheets is cooled off, eliminated internal stress;
(6) demoulding: with the composite conductive thin film material bipolar sheets of above-mentioned elimination internal stress and moulding by taking out in the mould.
Fig. 3 is bipolar cell of the present invention and package assembly sketch map thereof; Be coated with cream and be and smear negative electrode active material 4 and positive active material 5 on the conductive metal film 3 that covers on pressing and forming bipolar sheets two sides; Bipolar sheets places outer box 11 interior each bipolar sheets of battery to be separated by barrier film 6 and contiguous bipolar sheets; The bipolar cell both sides of being made up of bipolar sheets are anodal one pole sheet 7 and negative pole one pole sheet 8; Apply positive active material or negative electrode active material on anodal one pole sheet 7 or the negative pole one pole sheet 8, outer box 11 both sides of battery are provided with positive pole and draw pole 9 and draw pole 10 with negative pole.
Fig. 3 is a bipolar plates battery assembling sketch map, makes this kind battery and makes conventional batteries except different aspect the use of composite dual-electrode plates, and other do not have big difference basically.As shown in Figure 2, in the battery pack, bipolar substrate is by matrix 1, and inlays and the conductive particle 2 that is clipped between the conductive metal film 3 is formed.Positive active material 5 spreads upon on the matrix lead foil on one side, and 4 of negative electrode active materials spread upon on the lead foil of matrix another side.
Among Fig. 3, battery is formed by a plurality of single lattice cell stacks, and each single lattice battery separator 6 separates with contiguous single lattice battery, makes liner with having adsorbing ultra-fine fibre glass in the barrier film 6, and injects sulfuric acid as electrolyte.The active material of a both positive and negative polarity of single lattice battery will separate with the active material of the opposite electrode of adjacent cell.The installation of single lattice battery is as shown in Figure 2, but the outermost anodal one pole sheet 7 in entire cell both sides has active material with 8 needs one sides of negative pole one pole sheet.Specifically words; Just single lattice battery of anode terminal one side is having positive active material near adjacent single lattice one surface of battery; End plate one side near battery case 11 does not then have active material; Have only conductive film, both positive and negative polarity passes through pole end separately, and promptly positive pole is drawn pole 9, negative pole is drawn pole 10 and conductive film conduction.
This film composite material bipolar cell and bipolar plates matrix adopting thermosetting thereof or thermoplastic polyester and on bipolar substrate, embed conductive particle; Can produce a kind of life-span reaches 600 uses; And after the circulation of 80% deep discharge; Still can keep the high-energy lead-acid battery of initial capacity more than 85%, overcome the technological deficiency of current existence, and; The prepared bipolar film composite material lead-acid battery of the present invention has advantages such as corrosion resistant performance is good, in light weight, with low cost, and satisfies the extensive condition of making.
Claims (10)
1. film composite material bipolar cell and bipolar plates matrix thereof; Comprise matrix (1), the conductive particle (2) that places matrix (1) to be provided with is characterized in that: said matrix (1) is processed by thermosetting or thermoplastic polyester; Said conductive particle (2) places matrix (1) to distribute with latticed form; The conductive particle that is provided with (2) is at least one, and the diameter of said conductive particle (2) is greater than the thickness of matrix (1), and protrudes in the upper and lower surfaces of matrix (1); Said matrix (1) two sides is covered with conductive metal film (3); Said conductive metal film (3) contact with conductive particle (2) conduction of giving prominence on matrix (1) surface, and conductive metal film (3) obtains required bipolar sheets through precompressed, hot pressing, cooling, the demoulding, is assembled into two batteries that reach after bipolar sheets is coated with cream.
2. film composite material bipolar cell as claimed in claim 1 and bipolar plates matrix thereof; It is characterized in that: said conductive metal film (3) is through overlay film again after the surface treatment, and that said surface treatment comprises is inorganic, organic acid chemical treatment or polishing, polishing physical treatment, and conductive metal film (3) covers to go up through precompressed, hot pressing, cooling and the demoulding in substrate (1) and obtains required bipolar sheets; Said precompressed, hot pressing, cooling and the demoulding are all carried out in mould; Described hot pressing time is 1 to 20min, and pressure is 0.1 to 20MPa, and temperature is between 130 to 280 ℃; The type of cooling comprises natural cooling and water-cooled; Cooling time at 10s between the 30min, during the said demoulding in mould spraying help material, comprise general oiliness, neutrality, dryness release agent; Or carry out wax spray, spray demoulding silica gel, or plating mold release film material.
3. film composite material bipolar cell as claimed in claim 1 and bipolar plates matrix thereof; It is characterized in that: the described cream that is coated with is to smear negative electrode active material (4) and positive active material (5) on the conductive metal film (3) that covers on pressing and forming bipolar sheets two sides; Said bipolar sheets places interior each bipolar sheets of the outer box (11) of battery to be separated by barrier film (6) and contiguous bipolar sheets; The bipolar cell both sides of being made up of bipolar sheets are anodal one pole sheet (7) and negative pole one pole sheet (8); Said anodal one pole sheet (7) or negative pole one pole sheet (8) go up to apply positive active material or negative electrode active material, and outer box (11) both sides of battery are provided with that positive pole is drawn pole (9) and negative pole is drawn pole (10).
4. film composite material bipolar cell as claimed in claim 1 and bipolar plates matrix thereof is characterized in that: said thermosetting or thermoplastic polyester comprise one or more the combination in polyethylene, polypropylene, polybutadiene, polyphenyl dioctyl phthalate glycol ester and ABS powder and the section bar thereof etc.
5. film composite material bipolar cell as claimed in claim 1 and bipolar plates matrix thereof is characterized in that: said matrix (1) thickness is between 0.1 to 2mm.
6. film composite material bipolar cell as claimed in claim 1 and bipolar plates matrix thereof; It is characterized in that: said conductive particle (2) is processed by conducting metal and conductive non-metals material; Said conducting metal is lead material or glassy metal, and said conductive non-metals is a material with carbon element.
7. film composite material bipolar cell as claimed in claim 1 and bipolar plates matrix thereof is characterized in that: the volume ratio of said conductive particle (2) and matrix (1) is between 0.1% to 10%.
8. film composite material bipolar cell as claimed in claim 1 and bipolar plates matrix thereof is characterized in that: the size of said conductive particle (2) at 0.13mm between the 2.5mm.
9. film composite material bipolar cell as claimed in claim 1 and bipolar plates matrix thereof is characterized in that: the distance between the said conductive particle (2) is between 0.5 to 20mm.
10. film composite material bipolar cell as claimed in claim 1 and bipolar plates matrix thereof; It is characterized in that: the side distribution that the dot matrix of said conductive particle (2) distributes and can be employed in matrix; Both sides distribute simultaneously, and method such as two side portions distribution is carried out.
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| CN201210115319XA CN102623756A (en) | 2012-04-19 | 2012-04-19 | Bipolar battery made from thin film composite material and bipolar plate base of bipolar battery |
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| CN201210115319XA CN102623756A (en) | 2012-04-19 | 2012-04-19 | Bipolar battery made from thin film composite material and bipolar plate base of bipolar battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106104849A (en) * | 2014-03-06 | 2016-11-09 | 国际商业机器公司 | Ionic conduction composite diaphragm |
| CN104577132B (en) * | 2013-10-17 | 2016-11-16 | 北京好风光储能技术有限公司 | A kind of bipolar current collector and preparation method thereof |
| CN111370721A (en) * | 2020-03-19 | 2020-07-03 | 辽宁科京新材料科技有限公司 | Bipolar plate for flow battery |
| WO2022000308A1 (en) * | 2020-06-30 | 2022-01-06 | 宁德新能源科技有限公司 | Bipolar current collector, electrochemical device, and electronic device |
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| CN1592983A (en) * | 2001-01-19 | 2005-03-09 | 阿特拉沃达有限公司 | Electrode for a battery |
| US20090053601A1 (en) * | 2005-03-31 | 2009-02-26 | Kelley Kurtis C | Modular Bipolar Battery |
| US20100183920A1 (en) * | 2009-01-21 | 2010-07-22 | Advanced Battery Concepts, LLC | Bipolar battery assembly |
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| US4658499A (en) * | 1982-02-08 | 1987-04-21 | California Institute Of Technology | Bipolar battery plate |
| JPS58186168A (en) * | 1982-04-22 | 1983-10-31 | Furukawa Battery Co Ltd:The | Manufacturing method of grid base plate for storage battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104577132B (en) * | 2013-10-17 | 2016-11-16 | 北京好风光储能技术有限公司 | A kind of bipolar current collector and preparation method thereof |
| CN106104849A (en) * | 2014-03-06 | 2016-11-09 | 国际商业机器公司 | Ionic conduction composite diaphragm |
| US10770769B2 (en) | 2014-03-06 | 2020-09-08 | International Business Machines Corporation | Ion conducting hybrid membranes |
| CN111370721A (en) * | 2020-03-19 | 2020-07-03 | 辽宁科京新材料科技有限公司 | Bipolar plate for flow battery |
| WO2022000308A1 (en) * | 2020-06-30 | 2022-01-06 | 宁德新能源科技有限公司 | Bipolar current collector, electrochemical device, and electronic device |
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Application publication date: 20120801 |