CN101060178A - An electrolytic liquid for manufacturing the electric medium of storage battery and its manufacture method - Google Patents
An electrolytic liquid for manufacturing the electric medium of storage battery and its manufacture method Download PDFInfo
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- CN101060178A CN101060178A CNA2007101057026A CN200710105702A CN101060178A CN 101060178 A CN101060178 A CN 101060178A CN A2007101057026 A CNA2007101057026 A CN A2007101057026A CN 200710105702 A CN200710105702 A CN 200710105702A CN 101060178 A CN101060178 A CN 101060178A
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Abstract
The related electrolyte for accumulator comprises: 14-18wt% Na2OSiO2 with 30-39. 9% SiO2, 12-18% Na2SO4, 9. 95-11% Na2CO3, 0. 015-0. 03% poly-3-chlorobutylene, 0. 4-1. 2% polyaminosiloxanes, and the water. The preparation method comprises: putting the mixed material into a high-pressure container, sealing well, heating the container to 105-145Deg; when the pressure in container up to 30-64Kg/cm2, holding for 20-34h; cooling to room temperature to obtain the product containing ultra-fine particle. This invention is simple and environment friend.
Description
Technical field
The present invention relates to electrolytic solution that a kind of storage battery uses and preparation method thereof, particularly relate to the ultra tiny SiO that contains that a kind of storage battery uses
2Electrolytic solution of particle and preparation method thereof.
Background technology
Usually storage battery is electrolyte with the sulfuric acid solution and since sulfuric acid when mixing with water output a large amount of have corrosive white cigarette, cause pollution to human and environment.People are making great efforts to seek a kind of electrolyte of environmental protection always, produce a large amount of acid mists to overcome in producing the storage battery process, avoid human and environment is caused serious harm.
Making battery electrolyte is an important component part, and after housing, pole plate, dividing plate were fixing, the performance quality of storage battery had just depended on the electrolyte that charges into.And one of factor of decision electrolyte performance is exactly the performance of the electrolytic solution prepared, at present, in order to overcome the defective that above-mentioned electrolyte can produce a large amount of acid mists, the general battery electrolyte that adopts of people, mainly form with the Ludox modulation, for example: denomination of invention: " adopting low sodium silicate dielectric of storage battery attitude of magnetization technology preparation and uses thereof ", publication number: CN1391304A; This application relates to a kind of waterside with 15～25 weight portions and stirs the 40～60wt%SiO that contains that the limit joins 5～15 weight portions
2Ludox in, again through the low sodium silicate dielectric of storage battery attitude of magnetization preparation.Prepared dielectric is a kind of liquid electrolyte, and good fluidity had both overcome the defective that existing electrolyte produces a large amount of acid mists; Overcome the dielectric viscosity height of existing silicate again, brought the defective of difficulty for the can storage battery; Though improved the specific energy of storage battery widely with the storage battery of its liquid-state low-Na silicon salt dielectric making, but, because the defective of the composition of electrolytic solution own, so that easily dehydration and produce be full of cracks in use, cause that starting battery produces bulging, so that battery has just been scrapped, and this is a fatal defective.
Summary of the invention
One of purpose of the present invention: the electrolytic solution that overcomes existing sulfuric acid and be main component produces polarization through being internalized into after, can't clear up, and the big defective of electrolyte internal resistance of making;
Two of purpose of the present invention: overcome in the existing process of producing electrolytic solution, produce a large amount of acid mists harm people's the health and the defective of contaminated environment seriously;
Three of purpose of the present invention: overcome the existing storage battery of making through magnetized liquid-state low-Na silicon salt dielectric, dehydration and produce be full of cracks easily causes that starting battery produces bulging and then the defective that causes battery to scrap; Thereby provide a kind of ultra tiny SiO of containing of battery electrolyte that is used to make
2The electrolytic solution of particle.
Four of purpose of the present invention: in order to reduce the storage battery manufacturing cost and to reduce working strength of workers, make the workman avoid acid mist harm simultaneously, the production plant that makes the factory that produces storage battery become environment-friendly type provides a kind of preparation method of environment-friendly type.
The object of the present invention is achieved like this:
Provided by the inventionly be used to make that storage battery is dielectric contains ultra tiny SiO
2The electrolytic solution of particle, its component and content are:
A. the SiO that contains 30～39.9%wt
2Na
2OSiO
214～18%;
B.Na
2SO
4 12～18％；
C.Na
2CO
3 9.95～11％
D. poly-3-chlorobutylene
0.015～0.03%;
E. poly-amino silicone
0.4～1.2%;
F. surplus is a water; It more than is percentage by volume.
In above-mentioned technical scheme, described Na
2OSiO
2In the SiO that contains
2Particle diameter be 35～50nm.
Of the present inventionly contain ultra tiny SiO
2The preparation method of the electrolytic solution of particle may further comprise the steps:
1. contain ultra tiny SiO by above-mentioned
2The electrolytic solution of particle is formed weighing;
2. at first with the Na that weighs up
2OSiO
2Put into high-pressure bottle, add NaHSO then
4, poly-3-chlorobutylene, poly-amino silicone and water, mix;
3. good seal high-pressure bottle; adopt steam that high-pressure bottle is heated; be heated to 105～145 ℃; when the high-pressure bottle internal pressure is 30～64Kg/cm; kept 20～34 hours; outage naturally cools to room temperature then, promptly obtains being used to make the electrolytic solution with ultra-fine particlesization of battery electrolyte.
Provided by the inventionly contain ultra tiny SiO
2The electrolytic solution of particle has following characteristic: the pH value is 9～11, and its color is the light white liquid of transparent clarification.
In above-mentioned technical scheme, described Na
2OSiO
2In the SiO that contains
2Particle diameter be 35～50nm.
In above-mentioned technical scheme, described inorganic acid comprises: sulfuric acid or hydrochloric acid.
In above-mentioned technical scheme, described water comprises: distilled water, deionized water and pure water.
In above-mentioned technical scheme, described Na
2OSiO
2, Na
2SO
4, Na
2CO
3Poly-3-chlorobutylene, poly-its purity of amino silicone are more than the chemical pure.
The present invention has following effect:
Preparation method's technology of the present invention is simple, in process of production to human and environment all without any pollution, with after storage battery to environment also without any pollution, be a kind of production method of complete environmental protection.
The electrolytic solution with ultra-fine particlesization of the present invention's preparation is that a kind of pH value is 9～11; Its color is the slightly pale liquid of transparent clarification.Through high-temperature high-voltage reaction, molecule rearranges in process for preparation for it, and what resulting product presented is not the silicon salt electrolyte of colloidal, the magnetization silicon salt electrolyte of the emulsus that neither suspend, but the silicon salt liquid of clarification.Owing to done adjustment at the existing prescription of the relative the applicant of electrolytic solution prescription of the present invention, adopted SiO
2Particle diameter be the Na of 35～50nm
2OSiO
2As raw material, add Na again
2SO
4, and polymer, for example poly-3-chlorobutylene and poly-amino silicone, battery liquid can use the ionic condition silicon of ultra-fine particles like this, the synergy of it and other polymer, and solved the problem that accumulator internal resistance is diminished.Owing to add Na
2SO
4, reach the Na ion of storage battery specific demand, make the electrolytic solution alkalization; Also add poly-3-chlorobutylene, make electrolytic solution can from chemical change, obtain the chloride ion that dissociates, make the electrolytic solution alkalization equally, also add poly-amino silicone, effect is the effect of playing catalysis in chemical reaction, obtain ammonium ion simultaneously and make the electrolytic solution alkalization, so electrolytic solution reaches pH value 9～11.Therefore, the battery made from this electrolytic solution has the superperformance of silicon salt battery, and it and existing silicon salt battery compare, and the defective of both having avoided silicon salt battery molecule particle to cause greatly also has the advantage of lead-acid battery.The battery of being made by the electrolytic solution of this ultra-fine particlesization is after discharging and recharging; form the very fine and close pliable and tough colloidal film of one deck on each surface of electrolyte; for this reason; battery fully can spillage solution and gas; all electrochemical reactions are all carried out in the colloidal film; even battery goes wrong in the middle of using, do not need to do encapsulation process and can reach non-maintaining performance yet.And this film also forms on pole plate, so after battery used up, pole plate was also excellent, can recycling.This electrolytic solution uses in storage battery, and this electrolytic solution presents neutrality when the life of storage battery stops, and therefore abandoning scrap battery does not cause environmental pollution yet.So the battery of making of electrolytic solution of the present invention is in the recovery of material usefulness and have future difficult to the appraisal aspect the environmental protection again.Electrolytic solution based on ultra-fine particlesization is alkaline clear solutions; and the battery jar internal partition uses every cotton paper; so make that accumulator internal resistance is especially little; discharge capability with 30 times; charging ability then can reach 3C～4C; chargeable to more than 90% of capacity in 20 minutes, battery can use (as shown in Figure 1) as electric capacity, satisfies special requirement fully.The electrolytic solution of ultra-fine particlesization, molecule are very tiny, are about between the 5-50nm, thereby make this electrolytic solution highly stable, and when the discharge of big multiple, temperature rise also is very little.
The present invention preparation contain ultra tiny SiO
2The electrolytic solution of particle has integrated the strong point of plumbic acid electrolyte and silicon salt electrolyte, is the very good battery of a kind of performance with the storage battery of its making.
Below be accumulator property comparison with three kinds of different electrolyte fabrication:
| Battery types | Colloidal silicon salt battery | The glass fibre lead-acid battery | Receiving silicate battery of the present invention |
| Performance | Medium | Good | Very good (seeing accompanying drawing 1-8) |
| Big flow | Because with original dividing plate, the spacing between the pole plate is big, so capacity is low | Based on the glass fibre structure polar plate spacing from little, heavy-current discharge is less than 30 minutes to be finished, and | Because use every tissue paper, polar plate spacing can 30 times big flow discharges from minimum |
| Charging voltage | Low, internal resistance is big, acid concentration low, charge acceptance is low | High, internal resistance is less, the concentration height of acid, charge acceptance are strong, voltage seems rise fast | Height, it is fast that the internal resistance spy is little, charge acceptance strong, voltage rises |
| Residual current | Because charging voltage is low, the Retained aftercurrent is also low | Charging voltage height, residual current are high slightly | Charging voltage height, residual current are very high |
| It is long-pending to separate liquid | Height, in colloid, electrolyte does not flow | Low, immobilising in glass fibre | Low, electrolyte does not flow fully |
Description of drawings
Fig. 1 is to use the cycle life curve chart of the storage battery that the electrolytic solution of embodiment 1 makes;
Experimental condition wherein: discharging current: 0.42C;
Charging method: 16V constant voltage and current limiting 0.312C charging, 5.60, discharge capacity 70%;
Fig. 2 is the battery 30C discharge curve that the present invention makes;
Fig. 3 is the battery charge curve chart that embodiment 5 makes;
Fig. 4 is the electrokinetic cell discharge figure that embodiment 2 makes;
Fig. 5 is the silicon energy environment-friendly storage battery discharge characteristic curve that embodiment 5 makes;
Fig. 6 is the discharge curve of each hour rate of silicon energy environment-friendly storage battery of embodiment 5 making;
Fig. 7 is the silicon energy environment-friendly storage battery impulsive discharge characteristic curve that embodiment 5 makes;
Fig. 8 is the influence to capacity of embodiment 5 storage time of making and temperature.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in detail:
Present embodiment preparation contain ultra tiny SiO
2The electrolytic solution of particle:
Weighing accounts for the 34.95%SiO that contains of cumulative volume 14%
2Na
2OSiO
2, SiO wherein
2Particle grain size is 32nm;
Take by weighing the Na that accounts for cumulative volume 12%
2SO
4
Take by weighing the Na that accounts for cumulative volume 9.95%
2CO
3
Take by weighing the poly-amino silicone that accounts for cumulative volume 0.4%;
Take by weighing the 0.015% poly-3-chlorobutylene that accounts for cumulative volume;
Surplus is a distilled water; Above raw material is and adopts the chemical pure raw material of buying on the market.
Present embodiment is the preparation method may further comprise the steps:
1. at first with the above-mentioned Na that weighs up
2OSiO
2Put into high-pressure bottle, add Na successively
2SO
4, Na
2CO
3Poly-3-chlorobutylene, poly-amino silicone and distilled water mix;
2. seal high-pressure bottle; feeding steam in high-pressure bottle heats; be heated in 105～145 ℃ of temperature ranges all passable; when the high-pressure bottle internal pressure is 30Kg/cm; kept 20～25 hours; outage naturally cools to room temperature then, promptly obtains being used to make the electrolytic solution with ultra-fine particlesization of battery electrolyte.
The electrolytic solution with ultra-fine particlesization that present embodiment provides is used to make battery electrolyte is one to be the light white liquid of transparent clarification, and the pH value is 10.
1, in the electrolytic solution 10-20 parts by volume of the ultra-fine grain that embodiment 1 is prepared, add 30-60 parts by volume pure water and stirred 10 minutes, the proportion of measuring with densimeter is 0.89-1.09, and the HP value is 8-10;
2, getting the mixture adding sulfuric acid, the elder generation that prepare is sulfuric acid proportion furnishing 1.355-1.555, and again with sulfuric acid: mixture is to stir after 4: 1 ratios add, and its proportion reaches 1.26-1.29 and is advisable;
3, the mixed liquor that obtains is put into to be implemented the described drum of making of magnetic material or carries out molecule with high pressure 600V electric field to rearrange, thereby obtains the minimum fluid conductor of internal resistance.
4, with gained through polarization, the product of the step 3) after molecule rearranges is put into rotating speed again and is in 100-300 rev/min the mixer and stirs, get with straightway pump, directly irritate in the battery jar that assembles, the good seal storage battery, general charge weight is a lattice 9-14ml/Ah;
5, energising changes into conventional chemical synthesizing method to battery, changes into temperature to be: room temperature; Change into the time: 30-50 hour.
Wherein used battery case is box battery jar, and negative in lattice with common 17Ah green plate 5 positive 6, all the other are the same with the box accumulator structure of plumbic acid electrolyte fabrication, make a 2V100Ah, tight assembling is closed, and by the high frequency charge-discharge machine, 4 fill 3 changes into liquid after putting and change electrolyte into.The battery behavior performance (shown in Fig. 1,2 and 4) of making of the electrolyte and the formation method of present embodiment preparation: the discharge of (1) 10 hour rate reaches 105Ah; (2) 1 hour rates discharge 78Ah; (3) 1% constant currents are overcharged, and produce without any gas; (4) the shell inner periphery surface generates the pliable and tough colloid film of one deck densification, and all chemical reactions all carry out in film, and every polar board surface also forms such film simultaneously, thus can emergent gas, and liquid more can not overflow; (5) owing to the polar board surface film former, after electrolyte used up, it presented neutrality during battery end of life, and pole plate is intact, both can reuse, and is also free from environmental pollution.The recovery of these battery materials and high value is arranged aspect environmental protection.(6) based on ultra micro rice electrolyte, add and use in the battery that to make dividing plate Gu Neizute every cotton paper little, have 30 times of discharge capabilities, but the battery of 2V100Ah can discharge 8 seconds with 3000A, battery keeps that cell voltage returns to 2.06V after 1.2V5 minute, the 3000A that can reform discharged for 8 seconds, can repeat so not damage battery more than 3 times.The available big electric current 3-4C that charges is charged to 95% capacity in 30 minutes, can satisfy specific (special) requirements (adding power station etc. than later electric motor car).Made its temperature rise of product of ultra micro granulation electrolyte is atomic little.
Present embodiment preparation be used to make ultra tiny SiO of containing of battery electrolyte
2The electrolytic solution of particle adopts buy on the market chemical pure, contains 34.95%SiO
2Na
2OSiO
2, SiO wherein
2Particle grain size is 50nm, and weighing accounts for the Na of cumulative volume 16%
2OSiO
2Material; Purchase Na in market
2SO
4Account for 10.5%; , the chemical pure Na that on market, buys
2CO
3Take by weighing the poly-amino silicone of chemical pure 11%, that buy on the market that accounts for cumulative volume; Take by weighing the poly-3-chlorobutylene 0.02% of the chemical pure of buying on 0.8% the market that accounts for cumulative volume; Surplus is a distilled water.
Its preparation method may further comprise the steps:
1. at first with the above-mentioned Na that weighs up
2OSiO
2Put into high-pressure bottle, add Na successively
2SO
4, Na
2CO
3, poly-3-chlorobutylene, poly-amino silicone and distilled water, mix;
2. seal high-pressure bottle, feed steam and heat in high-pressure bottle, be heated in 105～145 ℃ of temperature ranges all passablely, when the high-pressure bottle internal pressure is 30Kg/cm, kept 20～25 hours, cutting off the power supply then naturally cools to room temperature, and promptly obtaining the pH value is 9; Color is transparent clarification electrolytic solution slightly pale liquid state, that have ultra-fine particlesization.Scheme as shown in Figure 4 with the electrokinetic cell discharge that present embodiment is made.
1, in electrolytic solution 15 parts by volume with the ultra-fine grain for preparing, add 46 parts by volume pure water and stirred 10 minutes, the proportion of measuring with densimeter is 0.89-1.09, and the HP value is 8-10;
2, get the mixture for preparing add hydrochloric acid or sulfuric acid, earlier the proportion of hydrochloric acid or sulfuric acid be between the furnishing 1.355-1.555 all can, again with inorganic acid: mixture is to stir after the ratio adding in 1: 4, and its proportion reaches 1.26-1.29 and is advisable;
3, mixed liquor is put into to rearrange through 600V above high voltage electric field molecule and makes the unobstructed internal resistance of ion motion passage minimum.Described electric field is an AC field, with high pressure 600V being that electric field polarizes.
4, after molecule rearranges, be to stir in 100-300 rev/min the mixer with step 3 gained, get, directly irritate in the battery jar that assembles with straightway pump being put into rotating speed, the good seal storage battery, general charge weight is a lattice 9-14ml/Ah;
5, energising changes into conventional chemical synthesizing method to battery, changes into temperature to be: room temperature; Change into the time: all could in 30 or 50 hours.
Employed storage battery be positive plate, the band lug of a box battery container that makes by lower bottom base and loam cake, band lug negative plate, electrolyte, use every cotton paper do that dividing plate Gu Neizute is little, cylinder manifold, joint pin; In the lower bottom base of described box battery container partition wall is set and is divided into lattice, general lattice number is 2 volt of one lattice, and the saddle of raised ribs shape is arranged on the lattice inner bottom surface, and pole plate is placed on the saddle; It is netted that described pole plate is made the regular hexagon honeycomb with lead or lead alloy, and scribble lead plaster on the positive and negative grid; Wherein negative, positive grid is with in alternate each lattice that is installed in the battery container base of cotton, do not interspace between the adjacent grid, positive and negative grid in the same lattice is together in parallel by the plate ear separately with cylinder manifold, positive and negative grid between the lattice dative is connected in series by joint pin respectively, is connected on the positive and negative pole; Build loam cake on the battery lower bottom base, fix with epoxy sealing again; Each lattice is filled the electrolyte (being again to change into liquid) that above-mentioned present embodiment is joined in the battery case, and remainder all steeps in changing into liquid the plate ear on pole plate.The battery charge characteristic curve of the storage battery that embodiment makes as shown in Figure 1, this battery 30C discharge curve is as shown in Figure 2.
The electrolytic solution with ultra-fine particlesization that is used to make battery electrolyte of present embodiment preparation adopts buy on the market chemical pure, contains 34.95%SiO
2Na
2OSiO
2, SiO wherein
2Particle grain size is 40nm, and weighing accounts for cumulative volume 18%; The Na that purchases in market
2CO
3Account for 11% of total amount; The chemical pure Na that on market, buys
2SO
4Take by weighing the poly-amino silicone of chemical pure 18%, that buy on the market that accounts for cumulative volume; Take by weighing the poly-3-chlorobutylene 0.03% of the chemical pure of buying on 1.2% the market that accounts for cumulative volume; Surplus is a distilled water.
The method of present embodiment preparation may further comprise the steps:
1. at first with the above-mentioned Na that weighs up
2OSiO
2Put into high-pressure bottle, add NaHSO successively
4, poly-3-chlorobutylene, poly-amino silicone and distilled water, mix;
2. seal high-pressure bottle, in high-pressure bottle, feed steam and heat, be heated in 120～145 ℃ of temperature ranges all passable, when the high-pressure bottle internal pressure is 64Kg/cm, keep 22 or 23 hours all can, then the outage naturally cool to room temperature, promptly obtaining the pH value is 11; Color is transparent clarification electrolytic solution slightly pale liquid state, that have ultra-fine particlesization.
The battery charge curve that present embodiment is made as shown in Figure 3; Discharge characteristic curve as shown in Figure 5; The discharge curve of each hour rate of storage battery as shown in Figure 6; Storage battery impulsive discharge characteristic curve as shown in Figure 3; Battery stores time and temperature are to the influence of capacity as shown in Figure 3.Fig. 7 is the silicon energy environment-friendly storage battery impulsive discharge characteristic curve that present embodiment is made; Storage time that Fig. 8 present embodiment is made and temperature are to the influence of capacity
Claims (6)
1. one kind is used to make the dielectric electrolytic solution of storage battery, and its component and content are:
A. the SiO that contains 30～39.9%wt
2Na
2OSiO
214～18%;
B.Na
2SO
4 12～18％；
C.Na
2CO
3 9.95～11％
D. poly-3-chlorobutylene 0.015～0.03%;
E. poly-amino silicone 0.4～1.2%;
F. surplus is a water, more than is percentage by volume.
2. by the described electrolytic solution of claim 1, it is characterized in that: described Na with ultra-fine particlesization
2OSiO
2In the SiO that contains
2Particle diameter be 35～50nm.
3. one kind prepares the described method that is used to make the dielectric electrolytic solution of storage battery of claim 1, may further comprise the steps:
A) form weighing by the described electrolytic solution of claim 1 with ultra-fine particlesization;
B) with the Na that weighs up
2OSiO
2Put into high-pressure bottle, add Na then
2SO
4, Na
2CO
3, poly-3-chlorobutylene, poly-amino silicone and water, mix;
C) good seal high-pressure bottle; adopt steam that high-pressure bottle is heated; be heated to 105～145 ℃; when the high-pressure bottle internal pressure is 30～64Kg/cm; kept 20～34 hours; naturally cool to room temperature then, promptly obtain being used to make the electrolytic solution with ultra-fine particlesization of battery electrolyte.
4. be used to make the method for the dielectric electrolytic solution of storage battery by the described preparation of claim 3, it is characterized in that: described water is distilled water, deionized water or pure water.
5. be used to make the method for the dielectric electrolytic solution of storage battery by the described preparation of claim 3, it is characterized in that: described Na
2OSiO
2, Na
2SO
4, Na
2CO
3, poly-3-chlorobutylene, poly-amino silicone raw material purity be the above reagent of chemical pure.
6. be used to make the method for the dielectric electrolytic solution of storage battery by the described preparation of claim 3, it is characterized in that: described Na
2OSiO
2In the SiO that contains
2Particle diameter be 35～50nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101057026A CN100541899C (en) | 2006-09-30 | 2007-05-25 | A kind of electrolytic solution of making battery electrolyte and preparation method thereof that is used to |
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|---|---|---|---|
| CN200610113581 | 2006-09-30 | ||
| CN200610113581.5 | 2006-09-30 | ||
| CNB2007101057026A CN100541899C (en) | 2006-09-30 | 2007-05-25 | A kind of electrolytic solution of making battery electrolyte and preparation method thereof that is used to |
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| Publication Number | Publication Date |
|---|---|
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| CN100541899C CN100541899C (en) | 2009-09-16 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324523A (en) * | 2011-08-26 | 2012-01-18 | 威海中创国际贸易有限公司 | Storage battery adopting new material of silicon liquid |
| CN102664288A (en) * | 2012-04-10 | 2012-09-12 | 浙江好运来集团有限公司 | Preparation method of environmentally-friendly storage battery |
| CN102709605A (en) * | 2012-04-10 | 2012-10-03 | 浙江好运来集团有限公司 | Electrolyte solution for preparing sodium silicate storage battery and method for preparing electrolyte |
| CN104505553A (en) * | 2014-11-25 | 2015-04-08 | 广州泓淮电子科技有限公司 | Environment-friendly lead-acid-battery regeneration-liquid concentrate and manufacturing method thereof |
| CN114464902A (en) * | 2021-12-01 | 2022-05-10 | 国网河北省电力有限公司电力科学研究院 | Long-life lead-acid storage battery |
-
2007
- 2007-05-25 CN CNB2007101057026A patent/CN100541899C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324523A (en) * | 2011-08-26 | 2012-01-18 | 威海中创国际贸易有限公司 | Storage battery adopting new material of silicon liquid |
| CN102324523B (en) * | 2011-08-26 | 2014-04-09 | 威海中创国际贸易有限公司 | Storage battery adopting new material of silicon liquid |
| CN102664288A (en) * | 2012-04-10 | 2012-09-12 | 浙江好运来集团有限公司 | Preparation method of environmentally-friendly storage battery |
| CN102709605A (en) * | 2012-04-10 | 2012-10-03 | 浙江好运来集团有限公司 | Electrolyte solution for preparing sodium silicate storage battery and method for preparing electrolyte |
| CN104505553A (en) * | 2014-11-25 | 2015-04-08 | 广州泓淮电子科技有限公司 | Environment-friendly lead-acid-battery regeneration-liquid concentrate and manufacturing method thereof |
| CN104505553B (en) * | 2014-11-25 | 2016-09-21 | 广州泓淮电子科技有限公司 | A kind of lead-acid accumulator regenerated liquid concentrated solution and preparation method thereof |
| CN114464902A (en) * | 2021-12-01 | 2022-05-10 | 国网河北省电力有限公司电力科学研究院 | Long-life lead-acid storage battery |
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| Publication number | Publication date |
|---|---|
| CN100541899C (en) | 2009-09-16 |
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