CN1636297A - Electrochemical cells and an interchangeable electrolyte therefore - Google Patents
Electrochemical cells and an interchangeable electrolyte therefore Download PDFInfo
- Publication number
- CN1636297A CN1636297A CNA018027768A CN01802776A CN1636297A CN 1636297 A CN1636297 A CN 1636297A CN A018027768 A CNA018027768 A CN A018027768A CN 01802776 A CN01802776 A CN 01802776A CN 1636297 A CN1636297 A CN 1636297A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- cell
- interchangeable
- battery
- deposition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
- C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
-
- 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
- H01M10/08—Selection of materials as electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
- H01M50/691—Arrangements or processes for draining liquids from casings; Cleaning battery or cell casings
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
An interchangeable electrolyte contains and additive that promotes interchangeable use between batteries and electroplating cells by limiting dendritic deposition in battery cells and promoting a smooth finish in an electroplating cell, such that fresh or spent electrolyte can be used interchangeably in these type of cells.
Description
Invention field
The present invention relates to comprise the electrochemical cell of secondary battery and electroplating cell, relate to and having with the electrolyte of therein additive to be supported in being used interchangeably of electrolyte between the different electrochemical cells.
Background technology
The defective that electrochemical cell ran into that adopts in electroplating process concentrates on the inhomogeneous deposition of metal on the negative terminal surface.Usually, higher electric current appears in the ledge on negative terminal surface, causes the accumulation at these regional metal crystal.These defectives are usually by overcoming in the electrolyte that a spot of leveling agent or brightener is added to electroplating cell.These can comprise natural rubber and resin or synthetic compound and mixture with similar plating performance.Typically, other additive also helps electroplating process.
In the situation of for example making active materials for use in secondary electrochemical cells of lead accumulator Battery pack, for example, the deposition of metal ion causes performance to reduce usually on negative pole, can cause battery pack to lose efficacy under extreme case.But in battery cell, when thinking that these influence battery performance nocuously, the employing of property-modifying additive is not satisfied.Anyone can not will have the used for electrolyte of the additive formulations that adopts in the plating in the lead accumulator group.
Advised in for example zinc-alkaline battery group, adopting some additive.For example, Rample has proposed quaternary ammonium polymer in US 3660170, rechargeable battery pack, and electroplating cell to prevent the formation of superfluous zinc dendrite on the negative plate of these electrochemical cells.But it does not indicate the interchangeable electrolyte of preparation.
Davis proposes some quaternary ammonium polymer in US3877993A, it is used for dry cell batteries to reduce the fixedly damage of these battery pack negative plates.Lewenstein proposes quaternary ammonium monomer in US3928066, it is used in the conventional lead accumulator group to prevent that hydrogen from discharging from negative plate, has reduced the loss of water from these battery pack thus.In addition, the proposal that does not prepare about interchangeable electrolyte.
From original technology, known the various electrolyte that are used for electroplating obviously, and known that other electrolyte prescription is used for battery cell.When the characteristic that suggestion generally occurs the surface at these electrochemical cell negative poles is made amendment, neither one proposes to be furnished with the electrolyte of following additives in these original measures: be applicable to simultaneously electroplating cell and battery cell mode, be applicable to the deposition that prevents the metal ion that sends from the electrochemical cell positive pole, electrolyte is interchangeable in these electrochemical cells like this.When sharing some composition, the general adjustment of these electrolyte is suitable for the specific purpose purposes.Up to now, for example, at battery cell with there is not the interchangeable electrolyte that can adopt continuously in the electroplating cell.At present, be considered to waste product with the battery pack electrolyte of crossing.Adopt interchangeable electrolyte that reusable chance is provided, help to think that from economic angle the circulation of battery pack electrolyte is suitable.
Summary of the invention
According to the present invention, a kind of electrochemical cell is provided, comprise positive pole, relative negative pole, the nonaqueous electrolytic solution that contacts with the negative pole ion and the metal ion that is used to prevent send from positive pole on negative pole electro-deposition to reduce or to prevent the deposition improver that the material of negative pole increases.
According to the present invention, provide the interchangeable electrolyte that can be used for simultaneously in battery cell and the electroplating cell.This interchangeability is to demonstrate the interchangeable surface activity of electrolyte deposition by adding to improve additive, has further prolonged battery pack useful life simultaneously, helps the smooth plating in electroplating cell.
In two kinds of purposes, demonstrating surface action is the key of interchangeability.In battery cell, demonstrated metal deposition and limited the battery pack life-span, and in electroplating cell, encouraged deposition, rather than avoided.Therefore, it has been generally acknowledged that to provide and be applicable to that electrolyte double-duty is impossible.Astoundingly, deposition improvement additive of the present invention had both prevented the dendritic growth in battery cell electrolyte, supported smooth plating when same used for electrolyte is in electroplating cell again, and refuse battery group acid solution can be reused in electroplating cell like this.When mechanism is not understood fully, find that additive helps more organized deposition in each case, this has limited dendritic growth, has increased the battery pack life-span under the situation of battery cell, under the situation of electroplating cell, help smooth leveling finish.Therefore, the electrolyte that contains additive is interchangeable employing when fresh or when recirculation.
According to the present invention, interchangeable electrolyte therefore contains the deposition improver, this deposition improver preferred type is ionic and is adsorbed onto the surface of negative pole, thereby prevents or the deposition on negative pole when having suppressed to derive from anodal metal ion being adsorbed onto negative pole in normal operating conditions.
Preferably, the deposition improver can comprise polarity aspect and nonpolar aspect so that have affinity for water and oil, fat etc.In addition, nonpolar aspect preferably includes alkyl and replaces it, and its blocking-up is from the ion of positive pole.
Electrochemical cell preferentially is a secondary battery, for example lead accumulator Battery pack, or electroplating cell, for example tin electroplating cell.Electrochemical cell can also be the gel electrolyte battery Battery pack.
The combination of electrolyte and deposition improver provide a kind of according to circumstances, based on suitable volume or by it being concentrated or dilution reaches up to it be used for secondary battery or electroplating cell is required or preferred specific gravity, be interchangeable electrolyte therefore between secondary battery and electroplating cell.
Under the situation of lead with sulfuric acid electrolyte or tin electrode battery pack, shown that n-alkyl dimethyl benzyl ammonium chloride and dioctyl sodium sulphosuc cinate are effective for the deposition that is suppressed on these electrodes, to increase the battery pack life-span, yet any sulfuric acid electrolyte that is used with these additives, no matter be fresh or, also can for example adopting interchangeably in the tin electroplating cell with crossing.
The present invention relates to provide a kind of method of the interchangeable electrolyte therefore in the electrochemical cell that is used in plating and battery pack, comprising: electrolyte is provided; Add the deposition improver to electrolyte, this improver and battery pack and electroplate the composition of electrochemical cell compatible, do not react with electrolyte or slow reaction and can be adsorbed onto negative pole so as to suppress or prevent to send from positive pole, be adsorbed onto the metal ion dendritic crystalline deposition thereon on the negative pole, promoted in the lip-deep smooth plating of electroplating cell.
The invention still further relates to a kind of electrochemical cell, this electrochemical cell have be deposited on battery pack composition that electrolyte in the electrochemical cell contacts on the deposition improver, like this when electrolyte adds in the electrochemical cell, the deposition inhibitor relevant with electrolyte will be adsorbed to negative pole, suppress or prevented in battery pack duration of work metal ion that send from positive pole, that be adsorbed onto negative pole deposition thereon, electrolyte can be interchangeably and/or is used for different electrochemical cells circularly after using.
Brief description of drawings
Fig. 1 illustrates a pair of schematic diagram that is used to estimate the electrochemical cell that the interchangeability effect that wherein adds the electrolyte that additive of the present invention is arranged is provided.
Detailed description of the invention
The present invention relates to the employing of the electrolyte of the type that deposits improver or additive and be used for electrochemical cell.Be defined as any solid or liquid reagent applicable to preferred group as the chemical compound of additive, when described reagent adds in the electrolyte of electrochemical cell, promoted the minimizing of the speed or the type of metal deposition on the negative pole of electrochemical cell, thereby provide the improvement of the quality and quantity aspect of electro-deposition, help the work of electrochemical cell, no matter it is as battery pack or electroplating cell.
Type applicable to the electrochemical cell that adopts with electrolyte of the present invention and additive comprises battery cell and electroplating cell, other battery types comprises electrolysis and electrolytic cell.
Consider battery cell and some electrolytic cell, advantage shows the raising of battery aspect in useful life.In electroplating cell and some electrolytic cell,, more smooth plate surface proves its advantage by being provided.For both, the interchangeability of electrolyte allows reusing and/or circulating in different application, has reduced the generation of waste liquid basically.From the using electrolyte for example can collect and be used for replenishing electroplating cell of battery pack, perhaps mix and be used in the new battery pack with fresh electrolyte.When electrolyte have basically as its only add help smooth plating or increase the material in battery pack life-span the time, it in addition realizing still keeping its value after the function first.
As mentioned above, the adding of additive in electrolyte provides the electrolyte easily with interchangeability.For example, comprise that the electrolyte sulfuric acid of additive of the present invention not only is applicable to the lead accumulator group but also be applicable to the tin electroplating cell, in electroplating cell, show by the advantage that contact provided between them.For this consideration, the electroplating cell of this reception does not need to get in touch with additive or get in touch with electrolyte usually when transmitting.
Preferable additives by compatible with the material of electrochemical cell, not with the electrolyte reaction or only with electrolyte very the organic compound of slow reaction constitute.Therefore the preferred molecule of organic compound has polarity aspect and nonpolar aspect, all has affinity for water and oil, fat etc.Successfully use individual metals not necessarily successfully to combine with other metal-electrolyte with the compound that indivedual electrolyte combine, therefore selecting mainly is by experience.But, as principle, can adopt organic compound with at least 8 carbon atoms, more preferably be to have from about 8 to 28 carbon atoms most preferably about 16 to 28 carbon atoms.As another kind of principle, can adopt those to have from the organic compound of about molecular weight of 250 to 550, be more preferably 350 to 450, the most about 400 to 410.Quaternary ammonium compound preferably.
Proved that the tin that is used in the sulfuric acid electrolyte and the organic compound of lead electrode comprise n-alkyl dimethyl benzyl ammonium chloride and dioctyl sodium sulphosuc cinate.Clearly, the former is that the cation latter is an anion in solution.
Other verified less important relatively compound comprises n-alkyl dimethyl benzyl ammonium sulfate, didecyl dimethyl ammonium chloride, didecyl methyl ethoxy ammonium propionate, and other quaternary ammonium compound of wide region, comprises pyrimidine and quinoline.Also proof can adopt amine, amine salt and amino-compound.N-alkyl dimethyl benzyl ammonium chloride is water base, and dioctyl sodium sulphosuc cinate is then based on methyl alcohol.
The structure of n-alkyl dimethyl benzyl ammonium chloride molecule is to be by the structural formula approximate representation:
R represents the n-alkyl substituent, simultaneously C
12, C
14And C
16Mixture.The structure of dioctyl sodium sulphosuc cinate is to be by the structural formula approximate representation:
R represents C
8Alkyl substituent.
Though the special mechanism how negative pole of reagent and electrochemical cell reacts is not also understood fully, possible explanation provides as follows as its effective use in interchangeable electrolyte is provided.
Think and play important effect in the process of the speed of the metal deposition of live part on restriction electrochemical cell negative pole of molecule and alkyl chain and type.
Alkyl substituent is generally " straight chain " hydrocarbon, and hydrocarbon is made of the wavy key of carbon atom, with C
8For example is expressed as follows:
Find that they can all stretch, be rolled into ball or with intermediate shape.Adjacent molecule typically self is arranged in them in the solution with suitable shape, so that the distance between the alkyl hydrogen atom is maximum.Though alkyl substituent is to repel water strongly and since charged " head " of this molecule for polar molecule for example glassware for drinking water affinity is arranged, so can be dissolved in water.
Comprise at reagent under the situation of Ionized molecule that they wish to be adsorbed onto on the negative terminal surface by Electrostatic Absorption in the mode similar to adsorbing metal ions.The degree of absorption depends on described electrochemical potentials.
Seem reasonably to be that the electric charge on n-alkyl dimethyl benzyl ammonium ion directly is adsorbed onto it on the negative terminal surface.Possible sulfo-butanedioic acid two hot radical ions and the intermediate state ions binding that is present in the electrolyte, bond is attracted to the surface of negative pole.
In case after the absorption, these reagent obviously exist the netted of alkyl chain or bulk state, these netted or bulks demonstrate and obviously prevent to have prevented to have got rid of the growth of dendrite at least to a certain extent from the entering of metal ion positive pole, that be adsorbed onto negative pole.
Find further that from the test of further carrying out n-alkyl dimethyl benzyl ammonium ion is adsorbed onto the end that is grown in the metallic crystal on negative terminal surface, sulfo-butanedioic acid two hot ions approach electrode surface absorption.
This phenomenon by after stretching operation by the outward appearance confirmation of electrode surface, what wherein micro showed under the situation of n-alkyl dimethyl benzyl ammonium crystal is deposited in appearance passivation significantly (blunted), and the sulfo-dioctyl succinate seems thinner (stringy).
Although different in appearance, the risk of sulfo-dioctyl succinate material is excluded, the weighing deposition materials, and demonstrating in both cases, deposition rate is very similar.
With reference to figure 1, realize that the equipment of wanting required for the present invention comprises electrochemical appliance 10, it comprises power supply 12 and one group of electrochemical cell 14.
The group of electrochemical cell 12 comprises first battery 16 and second battery 18.First battery 16 comprises positive pole 20, negative pole 22 and electrolyte 24.Be immersed in positive pole 20 and negative pole 22 in the electrolyte 24 or contact with electrolyte 24 easily.Second battery 18 comprises positive pole 26, negative pole 28 and electrolyte 30.Positive pole 26 is immersed in the electrolyte 30 with negative pole 28 or contacts with electrolyte 30 easily.Power supply 12 comprises cathode output end 32 and cathode output end 34.Power supply 12 provides the electric current of control size to first battery 16 and second battery 18, and they are connected to anodal 26, negative pole 28 with positive terminal 32 and are connected to mode anodal 20, that negative pole 22 is connected to negative terminal 34 and are connected in series.The electric current that this set has guaranteed to flow through first battery 16 as much as possible with the currents match that flows through second battery 18.
Can estimate that according to Faraday's law this has guaranteed that further the cell reaction that takes place closely cooperates in first battery 16 and second battery 18.
Functionally, unshowned electrochemical cell of the present invention will corresponding to battery 16 and comprise at least one positive pole corresponding to electrode 20, corresponding at least one negative pole of electrode 22, with the identical electrolyte of electrolyte 24 compositions.Typically, 16 beginnings of first battery do not have electrolyte.Typically, a part of electrolyte of extracting out from battery of the present invention is transferred in first battery 16, thereby is provided for the required content of its original function to first battery 16.
Similarly, the negative pole of battery of the present invention does not need identical construction, does not need to comprise identical element or metal with corresponding negative pole 22, do not need to comprise yet any can be with equal proportion total element or metal.
Subsequently, from the battery of present device, extract appropriate amount out and transfer to first battery 16, provide battery 16, the second batteries 18 with required electrolyte 24 to have the electrolyte 30 of appropriate amount thus, the amount of electrolyte derives from any basically known agent described herein.
Anodal 20 and 26 tin that typically comprise above 90wt%, negative pole 22 and 28 typically has 60: 40 to 50: 50 tin-lead solder compositions.Generally wire electrode was reeled before implanting battery 16 and 18, typically wire electrode has 10 millimeters filament diameter, at least 30 millimeters in the space between positive pole 26 and negative pole 28.Electrode 20 and 22 is set to be provided with coupling respective electrode 26 and 28.
Think that electrochemical cell 16 and 18 respectively comprises the electrolyte of about 100 ml volumes routinely. Battery 16 and 18 and their part dimension can amplify or dwindle, and can change in quantity.
In following example, describe use the said equipment and realized effect of the present invention.
Example 1
Copy the contrast of five kinds of electrolyte samples of five kinds of samples that extract from the difference source. Electrochemical cell 16 and 18 is electrically connected in series, and is connected in series corresponding to other three batteries and battery 16 and 18 battery 16, that have corresponding to the electrode of electrode 20 and 22 thus.Force power supply 12 that the voltage that amounts to 21/2 times of two battery required voltage is provided, the electric current in circuit remains unchanged.
All five positive poles by diameter be 2 millimeters, each heavy 10.00g, 97: 3 tin-silver solder silk constitute.All five negative poles by diameter be 3.2 millimeters, each heavy 10.00g, 50: 50 tin-lead solder silk constitute.
Electrochemical cell is a serial number, numeral 1 expression battery 18, and numeral 2 expression batteries 16, numeral 3,4 and 5 is illustrated in three other in battery pack batteries.
From being the same containers of 1.250 battery pack level sulfuric acid, proportion obtains 100 milliliters measuring samples.Except electrolyte 1 only injects the water, each of five samples injected 1.5 milliliters of water that contain various additives.1.5 it is 101.5 milliliters that the milliliter additive rises to the electrolyte volume of all five batteries, small but reduced proportion equably.
After adding, battery 1 contains the simple sulfuric acid in water.Battery 2 contains the n-alkyl dimethyl benzyl ammonium chloride that in the water acid of same amount adds 300/10000ths (ppm) up to a hundred.Battery 3 comprises the n-alkyl dimethyl benzyl ammonium sulfate of 300ppm.Battery 4 comprises the didecyl dimethyl ammonium chloride of 300ppm.Battery 5 comprises the dioctyl sodium sulphosuc cinate of 300ppm.
Take by weighing the weight of negative pole after 36 hours at electrochemical activation:
All electrode 10.0g before the test
Negative pole 2 10.74g
Negative pole 3 10.81g
Negative pole 4 10.95g
Negative pole 5 10.74g
By preceding described pure as can be seen electrolyte electrode many 0.99g.And the electrode that is exposed to additive of the present invention has increased weight still less.N-alkyl dimethyl benzyl ammonium chloride and dioctyl sodium sulphosuc cinate demonstrate has the equal effect that increases minimum weight in equal proportion, has probably descended 25%.
Because some that have gas in both positive and negative polarity produce, and look possible that deduction is: the difference in electrode measurement weight owing in processing procedure from the chemical equivalent of at least a portion hydrogen of negative pole.
Very poor fine hair shape coating appears in the surface of electrode 1, and coating more closely appears in electrode 4 and 5, the coating that electrode 2 and 3 appearance have the electrode mirror-quality of system's adjusting fully.
Example 2
Copy the contrast of three kinds of electrolyte samples of three kinds of samples that extract from the difference source.The 3rd battery that adopts in test is similar to the mode of three additional battery that are used for embodiment 1, forces 1 that power supply 12 provides two battery required voltages doubly.
The positive plate of power lead accumulator Battery pack is taken out all three positive poles of formation.Grid contains 6% the antimony of having an appointment in lead.Paste is made of brown lead oxide.Though be difficult to the weight of coupling paste plate portion when positive battery group plate is taken apart, each has the weight of about 15g ± 0.5g can to weigh up three plates.
The electrodepositing speed of the lead on the negative plate in sulfuric acid electrolyte is quite slow.Utilize with embodiment 1 in those identical negative poles of being adopted carry out test first time, after 150 hours, discernible weight increase does not appear in any negative pole still.
Usually, has negative pole for plumbic acid submarine battery pack based on the grid structure of copper.This helps to make the battery performance maximization at a large amount of interdischarge intervals, meets the needs of submarine being obtained maximal rate.Because the electrochemical potentials of copper is at Cu
+++ 2e
-=+0.34V makes it than at Pb
+++ 2e
-=-0.13 volt lead " expensive ", so copper is adapted to its application.Do not having under the condition of tangible adverse effect, if keep charging current, pure copper negative pole can be incorporated in the lead accumulator group.The plumbous film that deposits on the copper electrode surface, this helps to set up the current potential that is suitable for conventional lead-acid battery Battery pack.
According to the above, so negative pole made by the Copper Foil with bright reflecting surface, and before three samples of electrolyte were injected into three batteries practically simultaneously, battery pack was fully assembled, connected, and applies energy.
The electrolyte of battery 6 has the identical composition of electrolyte with the battery 1 of embodiment 1.The electrolyte of battery 7 has the identical composition of electrolyte with the battery 2 of embodiment 1.The electrolyte of battery 8 has the identical composition of electrolyte with the battery 5 of embodiment 1.
The structure of battery pack is convenient to that the anticathode plate carries out visual observation through tested person the time, and after several hrs, the visible dark space on the polar board surface becomes obvious.By can obviously observing this dark space with the dark red painted and brightness on the negative plate surface of obvious burnt hair sharp contrast and by the lead that plates with derive from the dark space that anodal antimony produces.
After the outward appearance of all negative plates stood significant change 24 hours, it is very dark that electrode 6 seems, only shows slight coppery in the black border; Electrode 7 shows the slightly coppery of grey; Electrode 8 seems and shades slightly than electrode 7, but shows the many of coppery than electrode 6.
Relatively easily infer from these phenomenons, be higher than significantly on electrode 7 and 8, be higher than on the limit on the electrode 7 at the electrodepositing speed on the electrode 8 at the electrodepositing speed on the electrode 6.
Embodiment 3
Two 6 volt of 105 identical class moldeed depth circulation lead-acid battery groups are carried out BatteryCouncil International Deep Cycling Battery Test Procedure (5/93).Test is at room temperature carried out, and about 7 months is one-period.Charging current is 30 amperes, and the voltage limit value is the 2.55V/ battery, up to turning back to 130% of discharge capacity formerly.Discharge at 75 amperes, up to the voltage limit value be the 1.75V/ battery.Before circulating, battery pack was had a rest 4 hours next time.
The test program that is applied to battery pack 1 and battery pack 2 begins simultaneously and finishes, and the very approaching placement of two battery pack is to guarantee any variations in temperature equilibrium.Finish 414 circulation time battery pack 1 inefficacies, battery pack 2 is finished 422 circulations at this moment.Two battery pack finish to test and take apart.
Select corresponding battery in all cases, disperse element wherein carefully.Six negative plates that derive from a battery of battery pack 1 are weighed to guarantee that any material that plates is included in the measurement with the dividing plate that links to each other with them with six negative plates that derive from battery pack 2 respective battery.
Battery pack 1 (common) battery pack 2 (additives)
374.4g 375.0g
403.8g 374.5g
396.8g 373.4g
401.2g 379.6g
400.0g 372.4g
389.4g
371.8g
(394.3g on average) 374.5g (on average)
Undoubtedly, therefore above-mentioned battery pack can think that with the standard manufacture of strictness their each battery lead plate assembles the weight that has much at one when test program begins.Like this, the negative pole that increases than the battery pack 2 after handling of the experience coating weight of the negative plate of undressed battery pack 1 exceeds 5%.
Example 4
The negative pole concentration that the negative pole that adopts with example 1 is identical is that 50% n-alkyl dimethyl benzyl ammonium chloride layer covers, and reaches electrode when being about as much as use and is immersed in degree in the electrode solution.This equals about 36 millimeters length.
Apply operation comprise with electrode vertically horizontal plane hang, allow the applying liquid of the excess quantity that applied to drip from electrode.When electrode weight reached 10.03g, electrode overturn simply, no longer further dripped with the coat self that allows to form from the teeth outwards.After this, electrode was cured two hours with 120 ℃ (248 ℃) on stove.
After this, electrode is placed in the container that contains 100 ml waters,, stirs to remove coating as much as possible and to be dissolved in the water with seal of vessel.Afterwards, the muriatic concentration of n-alkyl dimethyl benzyl ammonium is determined by spectrophotometer method in 100 ml waters.Demonstrate 160/1000000ths concentration, this successfully corresponding in 100 ml waters, the concentration of the solution 50% of 0.98SG, heavy 0.03g, be equivalent to 153/1000000ths.
Clearly do not have the increase of weight, difference is inaccurate owing to what measure.But operation shows that really it is feasible that the additive of measuring consumption is applied to the known any part that will during normal use be immersed in the electrochemical cell in the electrolyte, but advantageously, before adopting electrolyte, takes suitable delay.Therefore, electrochemical cell can keep standby condition for this application, and the simple interpolation of electrolyte is that electrolysis additive mixture institute is only must work for activating.
Example 5
The electrolyte of known appropriate amount contain must concentration n-alkyl dimethyl benzyl ammonium chloride, to proportion, reach end value by simple evaporation and concentration just over 1.250 up to estimation proportion with 1.120.After this, when cooling, add entry and equal 1.250 up to proportion.Adopting volume in battery is that electrolyte after 100 milliliters this adjusting is tested according to the program of embodiment 1 explanation.Electrolyte provides basically the performance identical with battery 2.
This simple test shows electrolyte can utilize simple boiling mode to transfer to the tin electroplating cell so that desired concn to be provided from the lead accumulator group of for example discharge.From electrolyte, only removed water.The conversion equivalence can be added water to regulate required electrolyte.
When illustrating and having described the preferred embodiment of the present invention, be to be understood that for those of ordinary skills, under the condition that does not deviate from the scope of the invention, can carry out variations and modifications.
Claims (20)
1. interchangeable electrolyte that is used in battery cell and the electroplating cell, each battery has the positive pole and the negative pole that can contact with interchangeable electrolyte, and interchangeable electrolyte comprises aqueous electrolyte and improves additive in order to an amount of surface deposition that promotes the interchangeable employing in battery cell and electroplating cell.
2. according to the interchangeable electrolyte therefore of claim 1, wherein deposition improvement additive has reduced the dendrite electro-deposition on the battery cell negative terminal surface.
3. according to the interchangeable electrolyte of claim 1, wherein deposit this agent addition agent and help smooth plating in electroplating cell.
4. according to the interchangeable electrolyte of claim 1, wherein aqueous electrolyte is made of sulfuric acid and water.
5. according to the interchangeable electrolyte of claim 1, wherein deposition improvement additive is the organic compound with at least 8 carbon atoms.
6. according to the interchangeable electrolyte of claim 1, wherein deposition improvement additive is the organic compound with molecular structure of polarity aspect and nonpolar aspect.
7. according to the interchangeable electrolyte of claim 1, wherein deposition improvement additive is surface reactive material or surfactant.
8. according to the interchangeable electrolyte of claim 1, wherein deposition improvement additive is the organic compound with 8 to 28 carbon atoms.
9. according to the interchangeable electrolyte of claim 1, wherein deposition improvement additive is the organic compound with 16 to 28 carbon atoms.
10. according to the interchangeable electrolyte of claim 1, wherein deposition improvement additive is the organic compound with molecular weight from 250 to 550.
11. electrochemical cell, comprise positive pole, relative negative pole, be applicable to the moisture interchangeable electrolyte therefore of battery cell and electroplating cell, aqueous electrolyte is ion with negative pole and contacts, interchangeable electrolyte contacts with the deposition improver, be used to prevent that the electro-deposition on negative pole of the metal ion that sends from positive pole is used for the flat surface finish when in electroplating cell reducing or to prevent that the material of negative pole from increasing when in battery cell.
12. according to the electrochemical cell of claim 11, wherein deposition inhibitor be in essence ionic state and be adsorbed onto negative pole or be adsorbed onto the ionic state material of electrolyte and the ionic state material in electrolyte is adsorbed onto on the negative pole.
13. according to the electrochemical cell of claim 11, wherein deposits improver and comprise it being nonpolar alkyl substituent in essence, and blocking-up derives from anodal metal ion.
14. electrochemical cell according to claim 11, wherein electrochemical cell is secondary cell or electroplating cell, wherein depositing improver and electrolyte is interchangeable between secondary cell and electroplating cell, this exchange is based on identical volume, or by it being concentrated or diluting to reach the proportion of suitable each battery.
15. according to the electrochemical cell of claim 14, wherein secondary cell is the lead-acid battery Battery pack, electroplating cell is the tin electroplating cell.
16. according to the electrochemical cell of claim 15, wherein electrolyte is to have added as the n-alkyl dimethyl benzyl ammonium chloride of deposition improver or the dilute sulfuric acid of dioctyl sodium sulphosuc cinate.
17. the method that the interchangeable electrolyte therefore in the electrochemical cell that is used in plating and battery pack is provided comprises: electrolyte is provided; Add the deposition improver to electrolyte to form interchangeable electrolyte therefore, the composition of this interchangeable electrolyte and plating and battery pack electrochemical cell is compatible, do not react with electrolyte or slow reaction and can be incorporated into negative pole, so that at least a effect of selecting in the group that is made of following effects is provided: suppress or prevent from positive pole send the negative pole of metal ion the battery pack electrochemical cell on dendrite deposition, and promoted smooth plating on the plate surface in electroplating electrochemical cell.
18., further comprise from the battery pack electrochemical cell interchangeable electrolyte transferred to the plating electrochemical cell according to the method for claim 17.
19. according to the method for claim 17, further comprise from the battery pack electrochemical cell and remove interchangeable electrolyte,, add interchangeable electrolyte to the plating electrochemical cell by dilution or the concentrated proportion of regulating interchangeable electrolyte.
20. according to the method for claim 17, further comprise from the battery pack electrochemical cell and remove interchangeable electrolyte, interchangeable electrolyte is mixed with fresh electrolyte to form the interchangeable electrolyte of circulation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA200004112 | 2000-08-11 | ||
| ZA2000/4112 | 2000-08-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1636297A true CN1636297A (en) | 2005-07-06 |
Family
ID=25588861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA018027768A Pending CN1636297A (en) | 2000-08-11 | 2001-08-10 | Electrochemical cells and an interchangeable electrolyte therefore |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1410451A2 (en) |
| JP (1) | JP2004507046A (en) |
| CN (1) | CN1636297A (en) |
| AU (1) | AU782079B2 (en) |
| WO (1) | WO2002015297A2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104064816A (en) * | 2014-05-14 | 2014-09-24 | 超威电源有限公司 | Electrolyte additive for hydrogen evolution suppression of lead-acid storage battery and preparation method for electrolyte additive |
| CN105247728A (en) * | 2013-05-31 | 2016-01-13 | 约翰·C·菲特 | A metal accumulation inhibiting and performance enhancing supplement and a system for delivering the supplement |
| CN105474448A (en) * | 2013-08-08 | 2016-04-06 | 锡安能量公司 | Self-healing electrode protection in electrochemical cells |
| CN106025421A (en) * | 2016-08-12 | 2016-10-12 | 合肥国轩高科动力能源有限公司 | Electroplating peeling recovery technology of lithium battery electrode |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8728651B2 (en) * | 2010-08-30 | 2014-05-20 | Highwater Innovations, Llc | Low aspect ratio spiral-wound VRLA battery |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3660170A (en) * | 1970-04-08 | 1972-05-02 | Gen Electric | Dendrite-inhibiting additive for battery cell having zinc electrode |
| US4601847A (en) * | 1983-08-22 | 1986-07-22 | Macdermid, Incorporated | Composition for use in electroplating of metals |
| JPS61194194A (en) * | 1985-02-22 | 1986-08-28 | Keigo Obata | Tin, lead or solder plating bath |
| US4801511A (en) * | 1985-06-28 | 1989-01-31 | Union Oil Company Of California | Battery cell electrolyte |
-
2001
- 2001-08-10 JP JP2002520326A patent/JP2004507046A/en not_active Withdrawn
- 2001-08-10 AU AU83241/01A patent/AU782079B2/en not_active Ceased
- 2001-08-10 WO PCT/US2001/025019 patent/WO2002015297A2/en active IP Right Grant
- 2001-08-10 CN CNA018027768A patent/CN1636297A/en active Pending
- 2001-08-10 EP EP01962025A patent/EP1410451A2/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105247728A (en) * | 2013-05-31 | 2016-01-13 | 约翰·C·菲特 | A metal accumulation inhibiting and performance enhancing supplement and a system for delivering the supplement |
| CN105247728B (en) * | 2013-05-31 | 2019-01-08 | 约翰·C·菲特 | The system for inhibiting the supplement of metal accumulation and enhancing performance and delivering the supplement |
| CN105474448A (en) * | 2013-08-08 | 2016-04-06 | 锡安能量公司 | Self-healing electrode protection in electrochemical cells |
| CN105474448B (en) * | 2013-08-08 | 2019-03-22 | 锡安能量公司 | Selfreparing electrode protection in electrochemical cell |
| CN104064816A (en) * | 2014-05-14 | 2014-09-24 | 超威电源有限公司 | Electrolyte additive for hydrogen evolution suppression of lead-acid storage battery and preparation method for electrolyte additive |
| CN104064816B (en) * | 2014-05-14 | 2016-10-05 | 超威电源有限公司 | A kind of electrolysis additive of lead-acid accumulator suppression liberation of hydrogen and preparation method thereof |
| CN106025421A (en) * | 2016-08-12 | 2016-10-12 | 合肥国轩高科动力能源有限公司 | Electroplating peeling recovery technology of lithium battery electrode |
| CN106025421B (en) * | 2016-08-12 | 2018-09-18 | 合肥国轩高科动力能源有限公司 | A kind of plating stripping recovery method of electrode of lithium cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004507046A (en) | 2004-03-04 |
| AU8324101A (en) | 2002-02-25 |
| WO2002015297A3 (en) | 2003-01-09 |
| WO2002015297A2 (en) | 2002-02-21 |
| EP1410451A2 (en) | 2004-04-21 |
| AU782079B2 (en) | 2005-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS5928588A (en) | Inhibitor for dendrite of zinc | |
| CN1677725A (en) | Lead alloy and lead storage battery using it | |
| CN103477477A (en) | Negative electrode active material for a lithium secondary battery, and method for preparing same | |
| US4510218A (en) | Electrolyte for zinc-bromine storage batteries | |
| EP3199667A1 (en) | Method for producing silicon-plated metal plate | |
| CN103109412B (en) | Lead battery and be equipped with the idling stop vehicle of this lead battery | |
| CN107431204A (en) | Sodium ion and kalium ion battery anode | |
| US20230235476A1 (en) | Systems, devices, and methods for electroplated zinc negative electrodes for zinc metal cells and batteries | |
| CN103060846B (en) | Method for preparing Zn-Pb-Bi-La alloy electrode material through pulse electrodeposition | |
| Zhang et al. | Cyclic voltammetric studies of the behavior of lead-silver anodes in zinc electrolytes | |
| CN1636297A (en) | Electrochemical cells and an interchangeable electrolyte therefore | |
| JPS6313310B2 (en) | ||
| CN107022778B (en) | A kind of method of four sides nickel plating electrolytic copper foil and the tab of application this method production | |
| CN1266788C (en) | Alkaline secondary electrochemical generators with a zinc anode | |
| Jaiswal et al. | The combined impact of trimethyloctadecylammonium chloride and sodium fluoride on cycle life and energy efficiency of soluble lead-acid flow battery | |
| JP2005044759A (en) | Lead-acid storage battery and manufacturing method of the same | |
| US6821681B2 (en) | Electrochemical cells and an interchangeable electrolyte therefore | |
| JP2005025955A (en) | Lead acid battery and its manufacturing method | |
| US11108033B2 (en) | Electrochemical device and method for charging the electrochemical device | |
| EP1417357B1 (en) | Hydrogen evolution inhibiting additives for zinc electrowinning | |
| EP0109223B1 (en) | Electrolyte for zinc-bromine storage batteries | |
| US6440384B1 (en) | Composition for storage battery cells and method for making same | |
| CN115020700B (en) | Zinc sodium phosphate/zinc metal anode and preparation method thereof | |
| Raiford et al. | Increasing Lead Battery Performance Efficiency | |
| CN109638218A (en) | A method of improving zinc electrode corrosion resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |