CN102117938B - Energy-saving environmentally-friendly high-temperature valve-regulated sealed lead acid storage battery - Google Patents
Energy-saving environmentally-friendly high-temperature valve-regulated sealed lead acid storage battery Download PDFInfo
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Abstract
The invention provides an energy-saving environmentally-friendly high-temperature valve-regulated sealed lead acid storage battery. The battery comprises a lead-out post, a bus bar, a positive plate, a negative plate, an absorbed glass mat (AGM) separator, a battery jar and a safety valve, wherein 0.1 to 1.0 mass percent polyfluoro alkyl sulfonic acid is added into acidic electrolyte of the storage battery. According to the technical scheme, a high-temperature accelerated float charging life test result of the prepared valve-regulated sealed lead acid storage battery is shown as figures 11 to 13, and a high-temperature float charging loop test result of the prepared valve-regulated sealed lead acid storage battery is shown as a figure 14; and the battery has float charging life and loop life which are more than twice those of the conventional battery.
Description
Technical field
The present invention relates to valve controlled sealed lead-acid accumulator.
Background technology
Relatively other chemical power source and traditional lead acid batteries, valve controlled sealed lead-acid accumulator VRLA battery have advantages such as safety, low, non-maintaining, the no acid mist of cost leak, and power supply is widely used in communication base station at present in support.
Along with the develop rapidly in recent years of China Telecommunications Trade's mobile communication business, the mobile communication base station sum of three big telecom operators is above 1,000,000; According to statistics, the average year power consumption of each base station is about 1.5 ten thousand degree; Wherein 45% of the air-conditioning power consumption unit of accounting for base station power consumption total amount; Annual base station air conditioner power consumption surpasses 7,000,000,000 degree, is equivalent to 4,300,000,000 kilograms of CO2 emissions.Under the situation of energy growing tension, call and market development at present, realize the effect of energy-saving and emission-reduction, reduce air conditioning energy consumption and seem particularly necessary in order to respond country.Equipment mainly comprises two types of main equipment and corollary equipments in the base station machine room, and main equipment is generally BTS wireless device etc.; Corollary equipment has transmission, air-conditioning, power supply, storage battery etc.Base station BTS wireless device, transmission equipment, power-supply device, equal ability operate as normal under 40 ℃ of situation; Common valve controlled sealed lead-acid accumulator is the highest to temperature requirement, and the nominal serviceability temperature is 25 ℃, and storage battery can obtain longer life under 25 ℃ environment, and long-time running reduces half the if temperature raises 10 ℃ useful life approximately.Therefore on the basis of 25 ℃ of computer room temperatures, promoting 10 ℃～15 ℃ is battery system to influencing in the base station to maximum.Improve the serviceability temperature of storage battery, the development high-temperature battery can reduce the use and the energy consumption of air-conditioning, seems significant to reducing energy consumption of base station.For communication base station, temperature was once whenever being heightened, just can electrical energy saving 6%～8%, practice thrift the electricity charge at least 1.1 hundred million RMB, and temperature improves 10 ℃ of calculating, and the power consumption of whole equipment room will reduce by 60%～80%.If bring up to 35 ℃ to the base station air conditioner design temperature by present 25 ℃; And the float life of battery is compared not reduction with 25 ℃; Not only can practice thrift considerable electricity charge; And meet national energy-saving and emission-reduction industrial policy, but the life-span of common VRLA battery do not allow to do like this, have only high-temperature battery could satisfy this demand.
The internal structure of valve controlled sealed lead-acid accumulator is formed by drawing pole, bus-bar, positive plate, negative plate, AGM dividing plate (sulfuric acid electrolyte is adsorbed in the AGM dividing plate), battery case and safety valve.
Each battery has a utmost point crowd; Comprise several pieces positive plates, several pieces negative plates and several pieces dividing plates composition, utmost point crowd has positive and negative two exits, is welded to respectively on the stereotype and forms bus-bar; The corresponding positive and negative pole of drawing is respectively arranged, in order to be connected on the positive and negative bus-bar with external circuit.Draw between pole and the battery cover and seal and identify with two-layer fluid sealant.There is an aperture to be used for installing safety valve above the battery cover, to guarantee the fail safe of battery.Pack into after utmost point crowd compresses well through utmost point crowd compressive plate in the battery case, carry out the glue envelope again and make battery case and battery cover seal, just formed high-temperature battery through a series of special PROCESS FOR TREATMENT again after the sealing.
The VRLA battery has solved the problem that flooded batteries is brought, and battery is sealed as far as possible.The oxygen that positive plate produces is compound with the hydrogen of negative plate generation, returns inside battery with the form of water, periodically opens and closes through safety valve, and it is minimum to make hydrogen separate out.The advantage of this design of VRLA battery is non-maintaining, need not to add water, to the user bigger volumetric specific energy is provided.Because VRLA battery electrolyte volume is less than flooded batteries, and major part is absorbed in pole plate and the dividing plate, even the housing breakage takes place, electrolyte leaks outside also seldom.Even flooded batteries safeguards to have the water loss neither particular importance because of adding water, but the VRLA battery is not allow to add water to safeguard in whole useful life.Therefore as far as the VRLA battery, dehydration means capacitance loss.
The VRLA battery is in the floating charge process, and inside battery reacts as follows:
Anodal: oxidation reaction takes place, and oxygen is through dividing plate diffusion negative pole
H
2O→(1/2)O
2+2H
++2e
Negative pole: reduction reaction takes place
Pb+(1/2)O
2→PbO+H
2SO
4→PbSO
4+H2O
PbSO
4+2H
++2e→Pb+H
2SO
4
The anodal oxygen that produces is diffused into negative pole through partition pores, makes negative pole generation reduction reaction, thereby reaches the purpose of not dehydration of VRLA battery.VRLA battery oxygen is compound to bring following some factor will shorten the life-span of battery:
1, negative pole oxygen is compound, needs reverse charging current, and this has reduced cathode voltage, makes negative pole that undercharge and sulfation take place more easily.Compound when too high when negative pole oxygen, can cause negative pole charging wretched insufficiency, have a strong impact on the life-span of battery.
2, in the constant voltage floating charge process, the reduction of negative plate polarization makes positive pole be in higher float charge voltage, and like this: a) floating current increases, and b) the available power loss increases c) increase of positive plate corrosion-deformation.
3, when compound when reaching 100%, the polarization of negative pole is minimum and stable, the increase of other normal battery voltage all can cause the increase of cathode voltage because of battery short circuit in organizing causes, this causes thermal runaway more easily.
These shortcomings of VRLA battery can be following with the formal description of Arithmetic Formula:
Anodal polarization:
P+＝80mv*log(If-Ic)+Kp..........Eq.1
If: floating current; Kp: constant; Ic: positive grid corrosion current (being approximately 2%-4%If), can ignore.
The negative pole polarization:
P-＝-120mv*log(If-Io)-Kn...............Eq.2
Io: oxygen recombination current; Can represent as follows: Io=R* (If-Ic) ... ... .Eq.3
R: oxygen combined efficiency; Because more unnecessary acid is arranged, the R value is greatly about 0.9 in the new battery, but it is not stable, and when battery generation water loss, the oxygen combined efficiency improves, and the R value approaches 1.
When the R value equals 1, P-=-120mv*log (Ic)-Kn....Eq.2A
In the floating charge process, negative plate always is in polarization, and its absolute value can be released as follows according to Eq.2A always greater than 0:
Ic＞10^(-Kn/120).......Eq.4
Can know from Eq.4, require I on the one hand
CThe least possible, positive grid corrosion is minimum, on the other hand I
CBig as far as possible, negative pole is fully polarized, reduce sulfation, this is mutual contradiction.
During the lead-acid battery floating charge, battery polarization when the positive pole polarization can increase positive grid corrosion greater than 70mv, shortens the life-span of positive plate at 120mv-140mv.Even positive grid corrosion is not a problem, when the positive pole polarization when 60mv brings up to 120mv, floating current increases by 6 times, the temperature that this has promoted battery has increased the possibility of thermal runaway.
Pt (total)=P++P-........Eq.5 or P+=Pt-P-....Eq.5a.
When oxygen is compound when reaching 100%, make P-approach 0, so P+=Pt.
Yet afoul with the VRLA battery design is to adopt maximum oxygen compound for reducing water loss, causes negative plateization low, and anodal polarization is high.When a battery was short-circuited in the battery pack, the voltage of other good battery was along with rising in the group, and the rising of voltage drives the rising of electric current, according to Eq.1, and Eq.2, Eq.5 is at the I that ignores
CUnder the condition:
Pt2-Pt1＝80mv*log(If2/If1)+120mv*log(If2/If1)........Eq.5b
Here P
T1And P
T2Be meant the total polarization before and after being short-circuited.
When there not being compound tense, Eq.5b can be described below:
If2/If1＝10^((Pt2-Pt1)/200mv).....Eq.5c
When compound when reaching 100%, 120*log (Ic/Ic)=0, so Eq.5b can be described below:
If2/If1＝10^((Pt2-Pt1)/80mv)....Eq.5d.
See that from above the floating current sudden change of full composite battery wants obvious greater than there not being compound battery, and the sudden change of floating current more can be described below for example expressly.In 48 battery systems, when 1 battery is short-circuited, the float charge voltage of other 47 batteries improves 49mv.According to Eq.5c, Eq.5d calculates, and the floating current of 100% composite battery is not have 2.33 times of composite battery.It is thus clear that the VRLA battery to the sensitiveness of floating current considerably beyond flooded batteries.
As everyone knows, temperature increases quickens cell degradation, according to the Arrhenius equation; 10 ℃ of the every risings of battery temperature; Positive grid corrosion rate adds accompanies, and the float life of battery reduces by half, and that is to say to be 5-8 under common VRLA battery quality guarantee life-span 25 ℃ of conditions; Bring up to 35 ℃ when temperature, the life-span of common VRLA battery has only 2-4.The rising of same temperature can make battery oxygen combined efficiency descend, and the percentage of water loss of battery increases greatly, circulation so repeatedly, and final result causes the battery thermal runaway.
VRLA battery case material is generally selected the ABS material at present for use, and the heat distortion temperature of ABS is about 90 ℃.The assembling pressure of VRLA battery is generally bigger, and also there is certain air pressure in inside battery, and the rising of temperature makes the ABS intensity decreases, and this makes battery that bulging take place under hot conditions more easily.Under actual 55 ℃ of floating charges test, the bulging of ABS is probably at 1.5%-2%.The bulging of ABS groove causes the increase of floating current more easily, further causes thermal runaway.
Can know from above analysis, realize the long-life of the VRLA battery under the hot conditions, must solve 1) dehydration; 2) anode plate grid corrosion; 3) battery case bulging at high temperature.
Summary of the invention
Technical problem to be solved by this invention provides a kind of energy-conserving and environment-protective high temperature modification valve controlled sealed lead-acid accumulator, can under hot environment, keep the long life.For this reason, the present invention adopts following technical scheme:
The present invention includes and draw pole, bus-bar, positive plate, negative plate, AGM dividing plate, battery case and safety valve, the AGM dividing plate is meant superfine glass fibre partition board, adds the Polyfluoroalkyl sulfonic acid of mass percent 0.1%-1.0% in the acid electrolyte of said storage battery;
With inside battery air contact-making surface palladium metal catalyst is set outside the acid electrolyte of said internal;
The grid of the positive plate of said storage battery adopts slicker solder silicon ternary alloy three-partalloy, alloy component: tin 0.1%-1.0%, and silicon 0.01%-0.1%, surplus is plumbous, the grid of the positive plate of said storage battery is for the grid of employing process for stamping manufacturing and through Overheating Treatment;
It is base material that said battery case adopts with ABS, in the ABS material, adds N-phenylmaleimide 0.1%-10%, glass fiber 0.1%-10%, talcum powder 0.1%-10%, styrene-grafted maleic anhydride 0.1%-10%;
Said percentage is mass percent.
After adopting technique scheme; The valve-control sealed lead acid battery that makes carries out high temperature and quickens float life test result such as Figure 11-Figure 13; High temperature floating charge loop test result such as Figure 14 compare with conventional batteries, have float life and the cycle life of the conventional batteries compared more than 1 times.Battery normal operating temperature provided by the invention may be up to 35 ℃, compares the conventional batteries operating temperature and exceeds 10 ℃.
Description of drawings
Fig. 1 is the structural representation of high temperature modification valve controlled sealed lead-acid accumulator provided by the present invention.
Fig. 2 is the floating current control curve figure of traditional storage battery under 55 ℃ of ambient temperatures for valve controlled sealed lead-acid accumulator and the traditional valve controlled sealed lead-acid accumulator that adds Polyfluoroalkyl sulfonic acid.
Fig. 3 is the dehydration control curve figure of traditional storage battery under 55 ℃ of ambient temperatures for valve controlled sealed lead-acid accumulator and the traditional valve controlled sealed lead-acid accumulator that adds Polyfluoroalkyl sulfonic acid.
Fig. 4 is the floating current control curve figure of traditional storage battery under 55 ℃ of ambient temperatures for valve controlled sealed lead-acid accumulator and the traditional valve controlled sealed lead-acid accumulator that adopts Catalytic Oxygen chemical combination technology.
Fig. 5 is the dehydration control curve figure of traditional storage battery under 55 ℃ of ambient temperatures for valve controlled sealed lead-acid accumulator and the traditional valve controlled sealed lead-acid accumulator that adopts Catalytic Oxygen chemical combination technology.
Fig. 6 is the comparison diagram 60 ℃ of down positive grid corrosion, and wherein the left side is plumbous calcium tin casting grid, and the right side is slicker solder silicon casting grid.
Fig. 7 is the comparison diagram 60 ℃ of down positive grid corrosion, and wherein the left side is plumbous calcium tin casting grid, and the right side is the punching press grid of same alloy through heat treatment technics.
Fig. 8 is the comparison diagram 60 ℃ of positive grid corrosion, and wherein the left side is plumbous calcium tin casting grid, and the right side is a this patent punching press grid.
Fig. 9 is traditional ABS materials hot deformation temperature movement curve
Figure 10 is an ABS materials hot deformation temperature movement curve provided by the present invention
Figure 11 is that 55 ℃ of high temperature quicken float life test, the floating current control curve figure of storage battery provided by the present invention and traditional storage battery.
Figure 12 is that 55 ℃ of high temperature quicken float life test, the fluid loss control curve figure of storage battery provided by the present invention and traditional storage battery.
Figure 13 is that 55 ℃ of high temperature quicken float life test, the capacity control curve figure of storage battery provided by the present invention and traditional storage battery.
Figure 14 is 50 ℃ of loop tests, the cycle specificity control curve figure of storage battery provided by the present invention and traditional storage battery.
Embodiment
1, to the solution of water loss problem
It is relevant that the dehydration of battery and positive plate are analysed oxygen negative pole liberation of hydrogen, reduces positive plate and analyse oxygen and negative plate liberation of hydrogen, can reduce floating current, the minimizing dehydration.The measure that improves the liberation of hydrogen overpotential for oxygen evolution can reduce floating current, reaches the purpose that reduces dehydration.
1.1 electrolysis additive
Among the present invention, adding proportion is the Polyfluoroalkyl sulfonic acid of mass percent 0.1%-1.0% in battery acid electrolyte.This material is a kind of anion surfactant; Even in high current potential sulfuric acid solution, also can keep stable; It is adsorbed on the positive plate surface, has changed the double-decker of electrode/solution interface, thereby improves the overpotential that oxygen is separated out on the positive plate; Reduce the floating current of battery, reach the purpose that reduces water loss.
Select for use with a collection of positive plate, negative plate, dividing plate, cell through lid makes 6 semi-finished product batteries altogether, is divided into 2 groups, wherein irritates electrolyte sulfuric acid, called after conventional batteries for 1 group; In addition 1 group is filled in that to add mass percent in the electrolyte sulfuric acid be 0.1%-1.0% Polyfluoroalkyl sulfonic acid, called after polyfluorinated alkyl sulfonic acid battery.After electricizing activation rolls off the production line, under 55 ℃ of conditions, carry out high temperature floating charge contrast test with 2.25VPC, write down floating current every day 1 time, fluid loss of 42 days records obtains Fig. 2 and Fig. 3 according to numerical values recorded.Can know that by Fig. 2 and Fig. 3 the battery that adds Polyfluoroalkyl sulfonic acid can improve floating current and fluid loss.
1.2 Catalytic Oxygen chemical combination is technological
Catalytic Oxygen chemical combination technology is meant at inside battery precious metal material catalyst (as being installed on the safety valve) is set; The anodal a part of oxygen that produces before arriving at negative pole with the filling battery in the unnecessary hydrogen of the gas compartment directly by catalyst chemical combination; Its result has reduced the oxygen cycle efficient of inside battery, thereby makes the increase that the anode polarization reduces and negative pole polarizes.The oxygen that loses when this technology biggest advantage is inner loop can not lose from battery, and these oxygen can directly be combined to water again through catalyst, and are retained in inside battery, and Catalytic Oxygen chemical combination technology makes the corresponding reduction with floating current of battery dehydration.The catalyst of precious metal material described in the present invention is a palladium metal.
Select for use with a collection of positive plate, negative plate, dividing plate, cell through lid makes 6 semi-finished product batteries altogether.Through irritating electrolyte sulfuric acid, after electricizing activation rolls off the production line, be divided into 2 groups, install common safety valve for 1 group, the called after conventional batteries is installed platinum metal catalyst, called after Catalytic Oxygen complex technique battery for 1 group in addition on safety valve.Under 55 ℃ of conditions, carry out high temperature floating charge contrast test with 2.25VPC, write down floating current every day 1 time, fluid loss of 42 days records obtains Fig. 4 and Fig. 5 according to numerical values recorded.Can know that by Fig. 4 and Fig. 5 the battery of employing Catalytic Oxygen complex technique is compared conventional batteries and can effectively be improved floating current and fluid loss.
2, to the solution of positive plate gate etching problem
Grid has collector and the double action that supports active material in battery.According to the Arrhenius equation, 10 ℃ of the every risings of battery temperature, positive grid corrosion rate adds accompanies.If positive grid generation corrosion-deformation, the collector effect of positive grid will reduce greatly, and the performance of battery obviously descends.Therefore under the high temperature applied environment, the excellent corrosion that improves positive grid is important.
2.1 slicker solder silicon alloy
The present invention adopts more corrosion resistant slicker solder silicon ternary alloy three-partalloy as positive grid alloy material, alloy component (mass percent): tin 0.1%-1.0%, silicon 0.01%-0.1% (scope).Element silicon adds to can be so that grid alloy casting back crystal grain becomes big in the terne metal, and reduce at the grain boundary corrosion position, thereby make its corrosion resistance improve.It is the core that the interpolation of silicon has reduced the crystal grain forming core that its crystal grain becomes big reason, causes crystal grain thick.What below show is positive grid corrosion picture contrast after the high temperature accelerated corrosion life test of the same terms and time.
This experiment selects for use plumbous calcium tin positive grid and the slicker solder silicon positive grid of casting of casting to carry out the rotproofness contrast.At 60 ℃ of H
2(density: 1.304g/cm3), it is 1.35V-1.38V (relative Hg/Hg that above two grids are applied anode potential to SO4 solution
2The SO4 electrode), etching time is 2 months.After the end, make grid sample observing samples grid corrosion situation under metallomicroscope, the result obtains Fig. 6.Can know that by comparison diagram 6 adopt slicker solder silicon ternary alloy three-partalloy as positive grid alloy material, the relative lead-calcium-tin alloy of its corrosion resisting property is better.
2.2 heat treatment technics and stamping technology perfect adaptation
The polycrystalline corrosion of metal mainly is a grain boundary corrosion, and its corrosion is decided by the rotproofness and the number of grain boundaries of crystal boundary, and the crystal boundary in the polycrystalline metal can be divided into low-angle boundary and high-angle boundary, and wherein the latter can be divided into general high-angle boundary and corrosion resistant crystal boundary again.The corrosion resistant crystal boundary is often referred to those its ∑ values less than 29 heavy site battle array (CSL) crystal boundary, and high and energy is low because of its atomic arrangement degree of order has a high structural stability for this type of crystal boundary.Through changing alloying and adopting heat treatment can increase considerably the ratio of corrosion resistant crystal boundary in the alloy and the rotproofness that distribution can significantly improve the crystal boundary of polycrystalline material thereof.Through heat treatment, can reduce total number of grain boundaries.The heat treatment method that this patent provides: under 200 ℃ of-300 ℃ of temperature, place 10min-60min.
Stamping technology punching out grid tradition casting grid unit response area increases more than 1 times, and better active material conductivity and life-span are long.Efficient is high in process of production, and energy consumption is low, more environmental protection.Can obtain thick pole plate than common planar punching press grid and be used for fields such as reserve, energy storage, power, bigger unit response area is coated with the cream amount with more unit, reduces material consumption and energy consumption.
The reaction table area of punching press grid improves greatly, will reduce the pole plate internal resistance greatly, improves charge acceptance and discharge platform, specific energy and the specific power of pole plate.Improve 2-3 under unit volume and the weight approximately doubly, improve battery charge ability to accept and life-span.
This experiment selects for use cast positive grid and lead-calcium-tin alloy of plumbous calcium tin to adopt punching press grid behind heat treatment technics and the stamping technology to carry out rotproofness to contrast.At 60 ℃ of H
2(density: 1.304g/cm3), it is 1.35V-1.38V (relative Hg/Hg that above two grids are applied anode potential to SO4 solution
2The SO4 electrode), etching time is 2 months.After the end, make grid sample observing samples grid corrosion situation under metallomicroscope, the result obtains Fig. 7.
See that from the contrast picture punching press grid behind employing heat treatment technics and the stamping technology has better corrosion resistant performance.
Changing grid alloy, behind heat treatment technics and the stamping technology, 60 ℃ corrode 4 months after (1 month be equivalent to 1 year life-span), analyze.
This experiment selects for use cast positive grid and grid of the present invention of plumbous calcium tin to carry out the rotproofness contrast.At 60 ℃ of H
2(density: 1.304g/cm3), it is 1.35V-1.38V (relative Hg/Hg that above two grids are applied anode potential to SO4 solution
2The SO4 electrode), etching time is 4 months.After the end, make grid sample observing samples grid corrosion situation under metallomicroscope, the result obtains Fig. 8.
Grid float life computational methods are represented as follows: (by maximum corrosion 40%, grid lost efficacy)
Tradition grid: 1587 * 40%/285 * 4=8.9
Grid among the present invention: 829 * 40%/67 * 4=19.8
Slave plate gate etching rate calculations sees that be more than 1 times of traditional grid the useful life of the grid among the present invention.
3, the solution of battery case bulging problem at high temperature
Battery case is the reservoir vessel of VRLA battery; The common ABS material of general employing is as container; Under hot conditions, there is certain bulging in battery case owing to receive inside battery Hu pressure, makes pole plate no longer closely contact with dividing plate; Thereby have influence on the performance of battery, might cause thermal runaway under the ultimate attainment condition.It is base material that battery case of the present invention is selected for use with ABS; In the ABS material, add (mass percent) N-phenylmaleimide 0.1%-10%, glass fiber 0.1%-10%, talcum powder 0.1%-10%; Styrene-grafted maleic anhydride 0.1%-10%; It is structurally-modified that the cell through lid material is carried out intramolecule, thereby the groove cover material is not deformed under higher temperature and external force, thereby improve the anti-deformation of battery case under hot conditions.Common material improves 10 ℃-30 ℃ relatively.
Test material is made into the certain size batten according to GB, is placed on then on the dimension card thermal deformation tester specimen holder, and applies, treat that oil bath temperature slowly rises with corresponding counterweight pressure.Material be heated with the pressurized situation under deform, when deformation displacement arrives some definite values, note the temperature of oil bath.The temperature of this moment is exactly a heat distortion temperature.When different materials required to reach same distortion, needed temperature was different.
Can know that from Fig. 9 and Figure 10 this patent ABS has higher heat distortion temperature, be more suitable for using in hot environment.
According to above experiment, energy-conserving and environment-protective high temperature modification valve controlled sealed lead-acid accumulator of the present invention adopts following scheme:
With reference to Fig. 1, the present invention includes and draw pole 1, bus-bar 2, positive plate 3, negative plate 4, AGM dividing plate 5, battery case 6 and safety valve 7, add the Polyfluoroalkyl sulfonic acid of mass percent 0.1%-1.0% in the acid electrolyte of said storage battery;
With inside battery air contact-making surface the palladium metal material catalyst is set outside the acid electrolyte of said internal;
The grid of the positive plate of said storage battery adopts slicker solder silicon ternary alloy three-partalloy, alloy component (mass percent): tin 0.1%-1.0%, and silicon 0.01%-0.1%, the grid of the positive plate of said storage battery is for the grid of employing process for stamping manufacturing and through Overheating Treatment;
It is base material that said battery case adopts with ABS, in the ABS material, adds (mass percent) N-phenylmaleimide 0.1%-10%, glass fiber 0.1%-10%, talcum powder 0.1%-10%, styrene-grafted maleic anhydride 0.1%-10%.
Below above-mentioned energy-conserving and environment-protective high temperature modification valve controlled sealed lead-acid accumulator (in Figure 11-14, naming with high-temperature battery) and conventional batteries are tested and are contrasted.
Participate in the conventional batteries of contrast: GFM-500
55 ℃ of high temperature acceleration float life method of testings are following:
1, capacity test reaches the storage battery of rated value, after charging fully, in 55 ℃ ± 2 ℃ environment, with 2.25VPC trickle charge 42d;
2, behind the 42d storage battery is taken out, place 24h～36h, in 25 ℃ ± 5 ℃ environment, carry out a 1h and lead capacity test,, amount to 1 year life-span as a testing cycle by the method for regulation;
3, repeat 1,2, be lower than 80% and the test once more that 1h leads capacity, confirm still to be lower than off-test in 80% o'clock until battery capacity.
Can know from Figure 11-Figure 13: the present invention's ability environmental protection high temperature modification valve controlled sealed lead-acid accumulator is compared conventional batteries and is had the float life above 1 times, can satisfy 35 ℃ of life requirements under the operating temperature fully.
With reference to Figure 14,50 ℃ of loop test modes:
1, battery pack is with 10 hour rate currents discharge I=0.1C
10To 1.80Vpc x 24,25 ℃ ± 2 ° K of temperature;
2, with the charging of constant pressure and flow pattern, I=75 ± 0.7A, voltage 2.32 ± 0.005Vpc charging 8 hours is then carried out 12 hours floating charges, charging voltage 2.25Vpc, current limliting 75A;
3, in 12 hours with high-temperature cabinet in temperature increase to 50 ℃ ± 2 ° of K, constant temperature then;
In case air themperature is arranged to 50 ℃ ± 2 ° K in 4 high-temperature cabinets, just begin discharge, reach 1.80Vpc x 24 with 30 ± 0.3A current discharge to 2 hour or assembled battery total voltage, reach any one restrictive condition, discharge promptly stops;
5, with the charging of constant pressure and flow pattern, I=75 ± 0.5A, voltage 2.32 ± 0.005Vpc charging 22 hours;
6, repeat 4 and 5 ten times, as a cycle period.
Can know from Figure 14: energy-conserving and environment-protective high temperature modification valve controlled sealed lead-acid accumulator of the present invention is compared conventional batteries and is had the high-temperature cycle life above 1 times, can satisfy 35 ℃ of life requirements under the operating temperature fully.
Claims (2)
1. energy-conserving and environment-protective high temperature modification valve controlled sealed lead-acid accumulator; Comprise and draw pole, bus-bar, positive plate, negative plate, AGM dividing plate, battery case and safety valve, it is characterized in that adding in the acid electrolyte of said storage battery the Polyfluoroalkyl sulfonic acid of mass percent 0.1%-1.0%;
Said internal except that acid electrolyte, palladium metal catalyst is set with inside battery air contact-making surface;
The grid of the positive plate of said storage battery adopts slicker solder silicon ternary alloy three-partalloy, alloy component: tin 0.1%-1.0%, and silicon 0.01%-0.1%, surplus is plumbous, the grid of the positive plate of said storage battery is for the grid of employing process for stamping manufacturing and through Overheating Treatment;
It is base material that said battery case adopts with ABS, in the ABS material, adds N-phenyl maleimide 0.1%-10%, glass fiber 0.1%-10%, talcum powder 0.1%-10%, styrene-grafted maleic anhydride 0.1%-10%;
Said percentage is mass percent.
2. energy-conserving and environment-protective high temperature modification valve controlled sealed lead-acid accumulator as claimed in claim 1 is characterized in that said palladium metal catalyst is arranged on the safety valve of said storage battery.
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| CN102544452A (en) * | 2012-03-02 | 2012-07-04 | 陈振富 | Maintenance-free lead acid battery electrode group and I-shaped chip-packaging process |
| CN104064711A (en) * | 2014-07-01 | 2014-09-24 | 国家电网公司 | Electric storage device applied to electric lighting system |
| CN104091969A (en) * | 2014-07-14 | 2014-10-08 | 浙江南都电源动力股份有限公司 | Valve-controlled sealing lead-acid storage battery for starting and stopping of automobiles |
| CN106099229B (en) * | 2016-08-03 | 2018-12-07 | 湖北双登润阳新能源有限公司 | Lead-acid storage battery terminal sealing performance accelerated test method |
| CN111600078A (en) * | 2020-05-08 | 2020-08-28 | 衡阳瑞达电源有限公司 | Lead-acid storage battery electrolyte capable of preventing anode from being corroded and preparation method thereof |
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