CN102208694A - Flat zinc-nickel secondary battery with replaceable polar plates and electrolyte - Google Patents

Flat zinc-nickel secondary battery with replaceable polar plates and electrolyte Download PDF

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CN102208694A
CN102208694A CN2011101249573A CN201110124957A CN102208694A CN 102208694 A CN102208694 A CN 102208694A CN 2011101249573 A CN2011101249573 A CN 2011101249573A CN 201110124957 A CN201110124957 A CN 201110124957A CN 102208694 A CN102208694 A CN 102208694A
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positive
plate
electrolyte
battery
nickel
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李中揆
王勋业
卢国骥
曾崇泗
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10Energy storage using batteries

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Abstract

The invention discloses a flat secondary zinc-nickel battery with replaceable polar plates. The cathode is in a plate-type structure that a cathode active substance is attached to a metal plate or a metal bracket, and the cathode active substance coats the metal plate or the metal bracket or is positioned on the contact face with a positive plate; the anode is in a plate-type structure consisting of a foamed nickel current collector and a nickel hydroxide active substance, and the positive plate is coated by adopting a polypropylene penetrating ion diaphragm; the electrolyte is positioned between the positive and negative plates; and the upper and lower parts of each single battery shell are provided with pressure liquid valves. The battery has the advantages that: specific energy is high, raw material source is wide, production cost is low, the service life is long, the positive and negative plates are convenient to replace, the polar plates can be reclaimed and the battery is environment-friendly.

Description

A kind of replaceable pole plate and electrolytical flat zinc-nickel secondary batteries
Technical field
The invention belongs to the zinc-nickel cell technical field of structures.
Background technology
Existing zinc-nickel secondary batteries has the specific energy height and (reaches 60-85whKG -1), specific power (reaches 200-250wKG greatly -1); open circuit voltage height (1.75V); the working temperature scope of application big (20-60 ℃); but characteristics such as high current charge-discharge, raw material wide material sources, aboundresources; mature production technology; cost is low, and production is used, recovery all can reach environment protectment protection, produces electrokinetic cell and wind energy, solar energy storage battery and is with a wide range of applications.But zinc electrode growth dendrite arm, the electrode deformation problem seriously restricts the commercialization process of zinc-nickel cell.The new zinc nickel-based battery that making has extended cycle life becomes the urgent task of chemical energy-storage battery.People have researched and developed flow battery for this reason, as all-vanadium flow battery, and V during anodal the reaction 5+And V 4+Between redox, V during negative reaction 2+And the redox between the V3+.Active material between the both positive and negative polarity all is dissolved in the solution, and redox reaction occurs in (as graphite felt) on the inertia collector between the both positive and negative polarity, separates with amberplex between the both positive and negative polarity, avoids both positive and negative polarity electrolyte to mix in battery.Its technological core is the active material that carries out redox reaction, and all in electrolyte, battery electrode just as the place of reaction, is born by tank body and store active material.Because the flow battery current density is inhomogeneous, near the lug corrosion more obvious, influenced useful life of battery, in addition, battery when overcharging, electrolyte leakage easily, thus make battery early ageing.When battery is implemented twice laid, when dismounting separates, must destroy housing, do not accomplish to make the best use of everything.The power of flow battery separates with capacity, though the life-span is long, battery takes up room greatly, and electrolyte also need carry out constantly replenishing and changing, and this is the main feature of flow battery.As all-vanadium flow battery (US006764789), half liquid stream patent (CN101127393A) adopts a kind of Zn-Ni liquid batteries of device preparation such as liquid pump fluid reservoir, and for example patent 200810031488.9, make static single fluid flow battery, do not need pump and fluid reservoir negative pole zinc salt the dissolving and be stored in the electrolyte, when discharging and recharging, zinc salt and zinc are changed between electrolyte and collector.But they can not change pole plate and electrolyte.
Summary of the invention
Purpose of the present invention provides a kind of specific energy big for the above-mentioned defective that overcomes existing zinc-nickel secondary batteries existence just, the raw material wide material sources, production cost is low, the battery long service life, be convenient to change the both positive and negative polarity pole plate, change electrolyte, and can recycle pole plate, flat secondary zinc nickle battery that both positive and negative polarity pole plate and electrolyte are changed in free from environmental pollution being convenient to.
Purpose of the present invention is achieved by the following technical solution.
A kind of replaceable pole plate and electrolytical flat zinc-nickel secondary batteries, comprise positive and negative electrode, electrolyte and housing, it is characterized in that, the present invention's negative pole is set to be adhered to by metallic plate or metallic support the plank frame of negative electrode active material, and negative electrode active material envelopes metallic plate or metallic support or is located at contact-making surface with positive plate; Positive pole is set to the plank frame that nickel-containing material or nickel foam collector and nickel hydroxide active material are formed, and adopts the saturating ion diaphragm of polypropylene to coat on positive plate; Electrolyte is between the positive and negative electrode plate; At the upper and lower valve that respectively offers of each cell housing.
The housing of each cell of the present invention is set to be formed by two relative snappings of box body, and cell material is an insulator; The collector of negative pole is set to negative electrode active material and coats three-dimensional copper strips, and electrolyte adopts gel to envelope negative plate or between positive and negative pole plate contact-making surface; The external connection end of positive and negative electrode conduction pole is stretched out from the perforate on the box body, in connect end and be connected with the lug of positive and negative pole plate in the box body respectively.
The present invention's electrolyte is set to liquid.
The present invention's electrolyte is set to soak into electrolyte on the conductive felt class thing of bulk.
The present invention's box body is set to a framework, and positive and negative pole plate adopts that mechanical connection manner is corresponding to be connected on the framework; The exposed face of both sides that directly positive and negative pole plate is positioned at framework is as positive and negative electrode.
The present invention can connect two above battery positive and negative electrodes overlapping, forms the battery pile like bipolar battery.
The plate thickness of the present invention's positive and negative electrode is set to identical with anode-cathode distance.
The present invention is provided with the hydrophobic foams in gas bleeder valve.
The present invention respectively is provided with a projection by connecting at the snapping place of two box bodys, and the housing that encircles whole cell on the seam by two projections that connect is provided with the hoop band.
Advantage of the present invention is, it is low that battery has processing cost, and the positive and negative pole plate of battery is replaceable, it is easy to operate to change, battery long service life, the comprehensively advantage of the performance of primary cell and secondary cell.The present invention is applicable to that the mode of changing battery is the application scenario of motor vehicle energy supply mode.The battery of the present invention's assembling is not scrapped because of a certain parts accidental damage integral body, and the battery of genus normal abandonment is also mostly because anodal rotten loose result can continue again to use behind the replacing positive pole.Battery of the present invention has also avoided double polarity plate to be easy to corrode short circuit and the problem damaged, but the present invention also can form like bipolar battery group structure.
Further set forth content of the present invention below in conjunction with drawings and Examples.
Description of drawings
Fig. 1 is a band conductive electrode rod structure schematic diagram of the present invention;
Fig. 2 is that the present invention is directly with the structural representation of box body side as positive and negative electrode.
Embodiment
Embodiment sees Fig. 1, a kind of replaceable pole plate and electrolytical flat zinc-nickel secondary batteries, comprise housing and the positive and negative electrode electrolyte that is positioned at housing, the present invention is characterised in that the housing of each cell is set to two box bodys, 1,2 relative snappings and forms; And negative pole 3 is set to be adhered to by metallic support the plank frame of negative electrode active material, and the collector of present embodiment negative pole is set to three-dimensional copper strips, and the electrolyte 5 of negative pole is set to gel and is positioned at contact-making surface with positive plate; Anodal 6 electrolyte are set to the plank frame of nickel foam collector 4; Anodal 6 adopt the saturating ion diaphragm 16 of polypropylene to coat; Respectively offer a valve 9 up and down at each cell housing.In valve, be provided with hydrophobic foams 13 and hospitalize liquid.
Technical solution of the present invention also can directly be set to electrolyte 5 electrolyte or soak into electrolyte on the conductive felt class thing of bulk.
Among Fig. 1, the present invention's cell material is set to plastics, positive and negative electrode is conducted electricity the external connection end of pole 7,8 stretches out from the perforate on the box body, in connect end respectively be arranged on box body in the lug of positive and negative electrode be connected.The cell material plastics adopt projection 10 and 11 to be abutted against at the relative snapping place of two box bodys, and are lined with rubber blanket 12 anti-leakages in the seam mouth.On two box body projections 10 and 11 projections of forming, the seam 14 of encircling whole housing adopts special fastened tools envelope that hoop band 15 is arranged, and buckles disengagement to prevent box.
Embodiment two sees Fig. 2, and the embodiment of the invention also can be set to a framework 17 by box body, and positive and negative pole plate adopts that mechanical connection manner is corresponding to be connected on the framework, as adopting sunk screw 18 to connect at two ends up and down among the figure; Present embodiment directly is positioned at positive and negative pole plate the exposed face of both sides of framework as positive and negative electrode.This structure can overlap several cells, forms the battery structure that the bipolar battery performance is seemingly arranged.3a is the zinc metallic plate among the figure, and 3b is a negative electrode active material; 6a is anodal nickel plate, and 6b is a positive active material.The casket body frame frame material is set to non-conductor, is provided with rubber-covered pad 12 at the place of being abutted against of framework and positive and negative pole plate, and (arrow is the utmost point flow path direction of positive and negative electrode among the figure) drawn positive and negative electrode and just formed electric current after connecing.Several cell levels can be piled up the battery pack that becomes bipolar performance like this.Respectively offer a valve 9 up and down at each cell housing, electrolyte 5 is set to spawn.
The embodiment of the invention can be provided with identical with anode-cathode distance the plate thickness of positive and negative electrode.
Battery cathode collector of the present invention is the three-dimensional perforation holes brass band through zinc-plated processing, negative electrode active material is binding agents such as zinc oxide, zinc powder, conductive carbon black, CMC, PTFE, HPMC, PVA, slurrying is rolling, is pressed together on the collector, is immersed in the gel electrolyte after the oven dry.Gel electrolyte is that zinc salt, KOH, LiOH, NaOH gel are made.Gel has alkali resistance and conductivity is preferably arranged.
Battery plus plate current-collecting body is a nickel foam, with hydroxyl nickel, nickel oxide, cobalt protoxide, high temperature resistant resistance to oxidation conductive carbon black, add binding agents such as PTFE, HPMC, PVA, make slurry, be coated on the nickel foam, the oven dry compressing tablet is made positive plate, wraps up polypropylene grafted barrier film, uses as positive plate to be assembled or replacing usefulness.Positive plate should be encapsulated in the polybag stand-by.
Element cell can level or side direction be superimposed as the battery pack of required voltage.Install because positive/negative plate is a symmetry, the conduction pole makes the current density of positive/negative plate each several part even respectively by the two ends outlet of battery case, and the line of battery pack is convenient.Operation principle of the present invention is: nickel electrode is anodal, and zinc oxide and zinc active matter are negative poles.Electrolyte is spawn, and zinc salt, KOH, NaOH, LiOH, H are wherein arranged 2The colloidal electrolyte that the alkaline-resisting gel of O is formed.
Figure 2011101249573100002DEST_PATH_IMAGE001
The present invention makes the plate active material of zinc-nickel cell the frame mode of being convenient to change, adopt solid-state storage pole piece and electrolyte, do not need liquid storage tank and pumping installations, only need manually split out old battery pole plates, new battery pole plates is installed, can be recovered the function that discharges and recharges of battery.
It is the collector of negative pole that negative pole of the present invention adopts zinc-plated three-dimensional brass band, active material is a zinc powder, zinc oxide is also used binding agents such as CMC, HPMC, PTFE, the conductive carbon black of electroless lead plating, bismuth, make the hydrophobic conductive layer, formation is difficult for the negative plate of shedding, it is changed into and is wrapped in the gel electrolyte, forms negative el.Gel electrolyte is soluble zinc salt: Ba (OH) 2, NaOH, KOH, the agent of LiOH base gel form.
The preparation of positive plate: with high temperature resistance to oxidation graphite is conductive agent, and hydroxyl nickel powder, cobalt protoxide, PTFE, HPMC, PVA are binding agent, make slurry, be applied on the nickel foam, through heat drying, 20Mpa is pressed into positive plate, and seals up for safekeeping in plastic sealing bag stand-by.Positive/negative plate is installed on respectively in removable two half-cell boxes, positive pole installs polypropylene additional and connects the skill barrier film, both positive and negative polarity two halves battery case is that spiral-lock is good by certain setting pressure, adds that stator promptly becomes an element cell, and the capacity of battery can accomplish that 20Ah is to 200Ah.
The present invention adopts the negative pole manufacture craft that can repeatedly discharge and recharge, and positive and negative pole plate can pass through about 250-500 time discharging and recharging, and just deforms capacity attenuation.After predetermined volumes, can open battery case at capacity attenuation, with the negative plate that artificial method more renews, battery case can be reused.Negative plate that changes and positive plate can reclaim material, and pole plate is processing regenerated.When this part cost was made for the first time usually about 25%.The material of making battery is reusable, reaches resource circulation and utilizes purpose.
The present invention can adopt two electrode thicknesses identical, and the anode-cathode distance unanimity forms real plane-parallel capacitor.Box body side material of the present invention is set to conductor, be provided with insulation cushion at two box body snapping places, the side of two box bodys is respectively the conductive electrode of positive and negative electrode, conducting direction is flowed out by pole plate, and promptly the sense of current is vertical with pole plate, and it makes current density very even, not accumulation stack, make the internal resistance of cell very little, be beneficial to current flowing and can not produce thermal runaway, make the temperature range of battery applications broader.
The electric current of the embodiment of the invention two is entered by a side, flows out from another side, can be made up of several cell stacks according to the battery required voltage, forms battery pile, has had the structure like bipolar battery simultaneously.Battery pack whole battery group structure becomes simply, is easy to mounting or dismounting, reclaiming.Battery pole plates also is injected with certain hydrophobic gel sets electrode active material with outside the respective diaphragm parcel, allows it be difficult for getting loose when vibrations, and guarantees the circulation of gas.Battery pack is by the polylith pole plate and have compressibility, insulation cushion rubber and the good tight loop of nonconducting intensity are formed.An aperture can be arranged on the rubber washer of each element cell, load onto one-way relief valves, it is the aperture of battery maintenance and interpolation electrolyte.The superiority of this structure battery: it can not scrapped because of a certain parts accidental damage of battery integral body, and is many because anodal rotten loose result only needs to change positive pole and can continue to use when belonging to normal abandonment yet.

Claims (9)

1. a replaceable pole plate and electrolytical flat zinc-nickel secondary batteries comprise positive and negative electrode, electrolyte and housing, it is characterized in that, negative pole is set to be adhered to by metallic plate or metallic support collector the plank frame of negative electrode active material; Positive pole is set to the plank frame that nickel-containing material or nickel foam collector and nickel hydroxide active material are formed, and adopts the saturating ion diaphragm of polypropylene to coat on positive plate; Electrolyte is between the positive and negative electrode plate; At the upper and lower valve that respectively offers of each cell housing.
2. according to right 1 described replaceable pole plate and electrolytical flat zinc-nickel secondary batteries, it is characterized in that the housing of each cell is set to be formed by two relative snappings of box body, cell material is an insulator; The collector of negative pole is set to negative electrode active material and coats three-dimensional copper strips, and electrolyte adopts gel to envelope negative plate or between positive and negative pole plate contact-making surface; The external connection end of positive and negative electrode conduction pole is stretched out from the perforate on the box body, in connect end and be connected with the lug of positive and negative pole plate in the box body respectively.
3. according to right 1 described replaceable pole plate and electrolytical flat zinc-nickel secondary batteries, it is characterized in that electrolyte is set to liquid.
4. according to right 1 described replaceable pole plate and electrolytical flat zinc-nickel secondary batteries, it is characterized in that electrolyte is set to soak into electrolyte on the conductive felt class thing of bulk.
5. according to right 1 described replaceable pole plate and electrolytical flat zinc-nickel secondary batteries, it is characterized in that box body is set to a framework, positive and negative pole plate adopts that mechanical connection manner is corresponding to be connected on the framework; The exposed face of both sides that directly positive and negative pole plate is positioned at framework is as positive and negative electrode.
6. according to right 1 or 5 described replaceable pole plates and electrolytical flat zinc-nickel secondary batteries, it is characterized in that, can two above battery positive and negative electrodes connections are overlapping, form battery pile like bipolar battery.
7. according to right 1 described replaceable pole plate and electrolytical flat zinc-nickel secondary batteries, it is characterized in that the plate thickness of positive and negative electrode is set to identical with anode-cathode distance.
8. according to right 1 described replaceable pole plate and electrolytical flat zinc-nickel secondary batteries, it is characterized in that, in gas bleeder valve, be provided with the hydrophobic foams.
9. according to right 1 or 2 described replaceable pole plates and electrolytical flat zinc-nickel secondary batteries, it is characterized in that, one projection respectively is set by connecting at the snapping place of two box bodys, and the housing that encircles whole cell on the seam by two projections that connect is provided with the hoop band.
CN2011101249573A 2011-05-16 2011-05-16 Flat zinc-nickel secondary battery with replaceable polar plates and electrolyte Pending CN102208694A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102694210A (en) * 2012-06-08 2012-09-26 吉林卓尔科技股份有限公司 Zinc-nickel secondary sealed square alkaline battery and manufacturing method thereof
WO2014201741A1 (en) * 2013-06-19 2014-12-24 Li Dahe Lithium-ion secondary battery with replaceable electrode
CN104752072A (en) * 2013-12-25 2015-07-01 中国电子科技集团公司第十八研究所 Full-sealing nickel-carbon supercapacitor manufacturing method
CN105845966A (en) * 2016-02-03 2016-08-10 杭州伯坦科技工程有限公司 Pole plate separated lithium ion battery and manufacturing method thereof
CN109004255A (en) * 2018-07-06 2018-12-14 南通沃德材料科技有限公司 Electrochemical energy storage battery
CN109786797A (en) * 2017-11-10 2019-05-21 中国科学院大连化学物理研究所 A kind of zinc-nickel single flow battery anode activation method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1501530A (en) * 2002-11-19 2004-06-02 比亚迪股份有限公司 Lead dioxide coated carbon material, making method and zinc-nickel battery containing the same
CN201038254Y (en) * 2007-04-05 2008-03-19 蔡传禔 Flat plate type zinc-nickel accumulator
CN201655917U (en) * 2010-05-11 2010-11-24 刘建政 High performance zinc-nickel storage battery
CN202042564U (en) * 2011-05-16 2011-11-16 卢国骥 Flat plate type zinc-nickel secondary battery with replaceable electrode plate and electrolyte

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1501530A (en) * 2002-11-19 2004-06-02 比亚迪股份有限公司 Lead dioxide coated carbon material, making method and zinc-nickel battery containing the same
CN201038254Y (en) * 2007-04-05 2008-03-19 蔡传禔 Flat plate type zinc-nickel accumulator
CN201655917U (en) * 2010-05-11 2010-11-24 刘建政 High performance zinc-nickel storage battery
CN202042564U (en) * 2011-05-16 2011-11-16 卢国骥 Flat plate type zinc-nickel secondary battery with replaceable electrode plate and electrolyte

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102694210A (en) * 2012-06-08 2012-09-26 吉林卓尔科技股份有限公司 Zinc-nickel secondary sealed square alkaline battery and manufacturing method thereof
WO2014201741A1 (en) * 2013-06-19 2014-12-24 Li Dahe Lithium-ion secondary battery with replaceable electrode
CN104752072A (en) * 2013-12-25 2015-07-01 中国电子科技集团公司第十八研究所 Full-sealing nickel-carbon supercapacitor manufacturing method
CN104752072B (en) * 2013-12-25 2018-02-06 中国电子科技集团公司第十八研究所 The preparation method of hermetically sealed nickel carbon supercapacitor
CN105845966A (en) * 2016-02-03 2016-08-10 杭州伯坦科技工程有限公司 Pole plate separated lithium ion battery and manufacturing method thereof
CN109786797A (en) * 2017-11-10 2019-05-21 中国科学院大连化学物理研究所 A kind of zinc-nickel single flow battery anode activation method
CN109786797B (en) * 2017-11-10 2022-03-29 中国科学院大连化学物理研究所 Activation method for positive electrode of zinc-nickel single flow battery
CN109004255A (en) * 2018-07-06 2018-12-14 南通沃德材料科技有限公司 Electrochemical energy storage battery

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Application publication date: 20111005