CN102005613A - Colloid electrolyte of storage battery and preparation method thereof - Google Patents
Colloid electrolyte of storage battery and preparation method thereof Download PDFInfo
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- CN102005613A CN102005613A CN2010105270155A CN201010527015A CN102005613A CN 102005613 A CN102005613 A CN 102005613A CN 2010105270155 A CN2010105270155 A CN 2010105270155A CN 201010527015 A CN201010527015 A CN 201010527015A CN 102005613 A CN102005613 A CN 102005613A
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- electrolyte
- colloid
- whisker
- colliod
- accumulator
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- 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
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Abstract
The invention discloses a colloid electrolyte of a storage battery and a preparation method thereof. The colloid electrolyte of the storage battery mainly comprises silicon-containing jellies, flow improvers, colloid intensifiers, complex additives and electrolytic solutions, wherein the flow improvers and the colloid intensifiers are acicular nanometer crystal whiskers or acicular nanometer microfibrils of oxides. The colloid electrolyte comprises the following components by weight percent: 2.9%-14.9% of gelatinizing agents, 0.05%-1% of the flow improvers, 8.5%-15% of the complex additives, and the balance of dilute sulfuric acid solutions. The colloid electrolyte has good thixotropic flowability and jel stability and low colloid kinematic viscosity, greatly enhances the colloid pouring efficiency of the colloid electrolyte and the immersional wetting action of the colloid electrolyte on a partition plate and a polar plate, is used for assembling the colloid storage batteries with different applications, has simple preparation process, greatly improves the smoothness of colloid pouring, improves the immersional wetting of colloids on the partition plate and the polar plate inside the storage battery and enhances the colloid pouring speed and the electrochemical property of the storage battery.
Description
Technical field
The present invention relates to the preparation method of a kind of Colliod electrolyte for accumulator and Colliod electrolyte for accumulator.
Background technology
Existing colloid storage battery mainly adopts the valve control techniques, is a kind of in the enclosed accumulator.The colloidal electrolyte that is gel state does not flow in storage battery, thereby not leakiness acid, can prevent effectively that active material from coming off, and effectively suppresses the growth and the infiltration of lead dendritic crystal, reduces self-discharge of battery, extending battery life.Than the AGM valve controlling type accumulator, colloid storage battery in use has remarkable advantages.
But the sulfuric acid electrolyte common owing to the colloidal electrolyte ratio of viscosities of colloid storage battery use is a lot of greatly, and this has brought acid test for filling acid technology of battery; In addition, if the colloid insufficient strength may cause the colloid fragmentation when battery is subjected to sharp pounding or collision, battery performance is greatly descended.Though colloidal electrolyte has certain thixotropy, even under the high-speed stirred condition, its viscosity is still much bigger than bright sulfur acid electrolyte, and it is slow not only to irritate sour speed, and battery is difficult for filling, and in most cases needs the back to mend glue.Full-bodied colloidal electrolyte is difficult to evenly flow into inside battery utmost point group everywhere in the encapsulating process, causes battery capacity inconsistent.Because the flowability of colloidal electrolyte is poor, permeability also decreases, and colloidal electrolyte very likely causes dividing plate or pole plate to occur doing to the poor permeability of dividing plate, pole plate, has a strong impact on battery performance.No matter present existing colloidal electrolyte is nano silicon system or Ludox system, and its encapsulating flowability is all very poor, and battery serviceability and life-span are all far below expection.
Summary of the invention
The objective of the invention is to solve the encapsulating difficulty that has Colliod electrolyte for accumulator now and cause, the problem that encapsulating efficient is low, battery performance is poor, the life-span is short, and then a kind of Colliod electrolyte for accumulator and preparation method thereof is provided because of the mobile difference of encapsulating.
Colliod electrolyte for accumulator provided by the invention is made by containing silica gel agent, mobile improvement and gel reinforcing agent, compound additive and electrolyte.
The preparation method of Colliod electrolyte for accumulator provided by the invention comprises:
Step 1 will contain silica gel agent and be distributed to that to make concentration in 35～45% the sulfuric acid solution be 2.9～14.9% colloidal dispersion, 50 ℃ of following strong agitation 2～8 hours, obtain the dispersion liquid first;
Step 2, to be distributed in the affiliated colloidal dispersion first by mobile improvement and the gel reinforcing agent that acicular nanometer whisker or acicular nanometer fento are made, and adjust the amount of flow ability modifying agent in described mobile improvement and the gel reinforcing agent, make the amount of described flow ability modifying agent account for 0.05～1% weight portion of colloid amount, dispersed with stirring was reduced to room temperature after 4～8 hours, obtained dispersion liquid second;
Step 3 is dissolved into compound additive in the described dispersion liquid second, regulates described compound additive and consists of 8.5～15% weight portions that account for the colloid amount, stirs 1～4 hour, obtains the target Colliod electrolyte for accumulator.
Colliod electrolyte for accumulator provided by the invention can be used for assembling the storage battery (starting battery, fixed storage battery, traction battery) of different purposes, the preparation method of Colliod electrolyte for accumulator provided by the invention has the preparing process characteristic of simple, improved the fluency of colloid encapsulating greatly, improved the wettability of colloid, improved the chemical property of encapsulating speed and battery inside battery dividing plate and pole plate.
Embodiment
The specific embodiment of the present invention provides a kind of Colliod electrolyte for accumulator and preparation method thereof, and corresponding Colliod electrolyte for accumulator is made by containing silica gel agent, mobile improvement and gel reinforcing agent, compound additive and electrolyte; The preparation method of corresponding Colliod electrolyte for accumulator comprises: step 1, and will contain silica gel agent and be distributed to that to make concentration in 35～45% the sulfuric acid solution be 2.9～14.9% colloidal dispersion, 50 ℃ of following strong agitation 2～8 hours, obtain the dispersion liquid first; Step 2, to be distributed in the affiliated colloidal dispersion first by mobile improvement and the gel reinforcing agent that acicular nanometer whisker or acicular nanometer fento are made, and adjust the amount of flow ability modifying agent in described mobile improvement and the gel reinforcing agent, make the amount of described flow ability modifying agent account for 0.05～1% weight portion of colloid amount, dispersed with stirring was reduced to room temperature after 4～8 hours, obtained dispersion liquid second; Step 3 is dissolved into compound additive in the described dispersion liquid second, regulates described compound additive and consists of 8.5～15% weight portions that account for the colloid amount, stirs 1～4 hour, obtains the target Colliod electrolyte for accumulator.
Below by specific embodiment the present invention is specified.
Embodiment one:
The Colliod electrolyte for accumulator that this embodiment provides is made by following method: be 400m with the 2.9g specific area under constantly stirring
2The gas phase nano SiO of/g
2Progressively join concentration and be in 35% the 97.1g dilution heat of sulfuric acid, be warming up to 50 ℃ of strong agitation 2 hours, obtain the colloidal dispersion first; Under constantly stirring be that 10 nanometers, draw ratio are that 5 needle-like ZnO whisker joins in the dispersion liquid first, continue powerful the stirring 4 hours, reduce to room temperature, obtain dispersion liquid second the 0.05g diameter; Under stirring condition, 1g starch, 3g sodium sulphate and 4.5g phosphoric acid is dissolved into is dissolved in the dispersion liquid second in the dispersion liquid second, continue to stir 1 hour, obtain having the colloidal electrolyte of good thixotropic fluidity and gel stability.The contrast colloid viscosity that does not add the ZnO whisker is 1398mPa.s, and the colloid viscosity that adds the ZnO whisker is 174mPa.s.
Embodiment two:
The Colliod electrolyte for accumulator that this embodiment provides is made by following method: be 150m with the 10g specific area under constantly stirring
2The gas phase nano SiO of/g
2Progressively join concentration and be in 40% the 90g dilution heat of sulfuric acid, be warming up to 50 ℃ of strong agitation 4 hours, obtain 100g colloidal dispersion first; Under constantly stirring be that 20 nanometers, draw ratio are about 10 needle-like MgO whisker and join in the dispersion liquid first, continue powerful the stirring 6 hours, reduce to room temperature, obtain dispersion liquid second the 0.15g average diameter; Under stirring condition, 1.5g sucrose, 3.5g sodium sulphate, 0.05g cobaltous sulfate and 5.0g phosphoric acid are dissolved in the dispersion liquid second, continue to stir 2 hours, obtain having the colloidal electrolyte of good thixotropic fluidity and gel stability.The contrast colloid viscosity that does not add the MgO whisker is 2471mPa.s, and the colloid viscosity that adds the MgO whisker is 426mPa.s.
Embodiment three:
The Colliod electrolyte for accumulator that this embodiment provides is made by following method: be 100m with the 14.9g specific area under constantly stirring
2The gas phase SiO of/g
2Progressively join concentration and be in 45% the 85.1g dilution heat of sulfuric acid, be warming up to 50 ℃ of strong agitation 8 hours, obtain the colloidal dispersion first; Under constantly stirring be that 50 nanometers, draw ratio are that 20 needle-like glass micro-fibers joins in the dispersion liquid first, continue powerful the stirring 8 hours, reduce to room temperature, obtain dispersion liquid second the 1g average diameter; Under stirring condition, 3g glycerol, 5g sodium sulphate and 6.5g phosphoric acid are dissolved in the dispersion liquid second, continue to stir 3 hours, obtain having the colloidal electrolyte of good thixotropic fluidity and gel stability.The contrast colloid viscosity that does not add glass micro-fibers is 3219mPa.s, and the colloid viscosity that adds glass micro-fibers is 632mPa.s.
Embodiment four:
The Colliod electrolyte for accumulator that this embodiment provides is made by following method: be 350m with the 7.5g specific area under constantly stirring
2The SiO of/g
2It is in 37% the 92.5g dilution heat of sulfuric acid, to be warming up to 50 ℃ of strong agitation 6 hours that particle progressively joins concentration, obtains the colloidal dispersion first; Under constantly stirring be that 40 nanometers, draw ratio are about 15 ZnO whisker and join in the dispersion liquid first, continue powerful the stirring 5 hours, reduce to room temperature, obtain dispersion liquid second the 0.45g average diameter; Under stirring condition, 2g pentaerythrite, 4g sodium sulphate and 5.5g phosphoric acid is dissolved in the dispersion liquid second dissolves, continue to stir 1.5 hours, obtain having the colloidal electrolyte of good thixotropic fluidity and gel stability.The contrast colloid viscosity that does not add the ZnO whisker is 2092mPa.s, and the colloid viscosity that adds the ZnO whisker is 338mPa.s.
Embodiment five:
The Colliod electrolyte for accumulator that this embodiment provides is made by following method: be 150m with the 12.6g specific area under constantly stirring
2The SiO of/g
2It is in 42% the 87.4g dilution heat of sulfuric acid, to be warming up to 50 ℃ of strong agitation 3 hours that particle progressively joins concentration, obtains the colloidal dispersion first; Under constantly stirring, be that 30 nanometers, draw ratio are about 8 TiO with the 0.65g average diameter
2Whisker joins in the dispersion liquid first, continues powerful the stirring 7 hours, reduces to room temperature, obtains dispersion liquid second; Under stirring condition, 2.5g ethylene glycol, 6g sodium sulphate and 5g phosphoric acid is dissolved in the dispersion liquid second dissolves, continue to stir 2 hours, obtain having the colloidal electrolyte of good thixotropic fluidity and gel stability.Do not add TiO
2The contrast colloid viscosity of whisker is 3014mPa.s, adds TiO
2The colloid viscosity of whisker is 471mPa.s.
Embodiment six:
Under constantly stirring, be 220m with the 5.8g specific area
2The SiO of/g
2It is in 41.8% the 84.2g dilution heat of sulfuric acid, to be warming up to 50 ℃ of strong agitation 5 hours that particle progressively joins concentration, obtains the colloidal dispersion first; Under constantly stirring, be that 25 nanometers, draw ratio are about 12 Al with the 0.08g average diameter
2O
3Whisker joins in the dispersion liquid first, continues powerful the stirring 6.5 hours, reduces to room temperature, obtains dispersion liquid second; Under stirring condition, 1.5g tartaric acid, 3.9g sodium sulphate, 0.5g cobaltous sulfate and 4.8g phosphoric acid is dissolved in the dispersion liquid second dissolves, continue to stir 1.5 hours, obtain having the colloidal electrolyte of good thixotropic fluidity and gel stability.Do not add Al
2O
3The contrast colloid viscosity of whisker is 1645mPa.s, adds Al
2O
3The colloid viscosity of whisker is 181mPa.s.
Embodiment seven:
The Colliod electrolyte for accumulator that this embodiment provides is made by following method: be 180m with the 3.1g specific area under constantly stirring
2/ g and 2.7g specific area are 350m
2The SiO of/g
2It is in 39.8% the 94.2g dilution heat of sulfuric acid, to be warming up to 50 ℃ of strong agitation 7 hours that particle progressively joins concentration, obtains the colloidal dispersion first; Under constantly stirring, be that 10 nanometers, draw ratio are about 8 TiO with the 0.19g average diameter
2Whisker and 0.06g average diameter are that 50 nanometers, draw ratio are about 20 Al
2O
3Whisker joins in the dispersion liquid first, continues powerful the stirring 5.5 hours, reduces to room temperature, obtains dispersion liquid second; Under stirring condition, 1.5g tartaric acid, 1g starch, 3.5g sodium sulphate and 5.0g phosphoric acid is dissolved in the dispersion liquid second dissolves, continue to stir 4 hours, obtain having the colloidal electrolyte of good thixotropic fluidity and gel stability.Do not add TiO
2Whisker and Al
2O
3The contrast colloid viscosity of whisker is 1407mPa.s, adds TiO
2Whisker and Al
2O
3The colloid viscosity of whisker is 302mPa.s.
Embodiment eight:
Under constantly stirring, be 150m with the 3.0g specific area
2/ g and 2.9g specific area are 350m
2The SiO of/g
2It is in 39.6% the 94.1g dilution heat of sulfuric acid, to be warming up to 50 ℃ of strong agitation 7 hours that particle progressively joins concentration, obtains the colloidal dispersion first; Under constantly stirring be that to be about 10 glass micro-fibers and 0.05g average diameter be that 50 nanometers, draw ratio are about 20 Al for 15 nanometers, draw ratio with the 0.20g average diameter
2O
3Whisker joins in the dispersion liquid first, continues powerful the stirring 5.5 hours, reduces to room temperature, obtains dispersion liquid second; Under stirring condition, 1.5g starch, 1g sucrose, 3.5g sodium sulphate and 5.0g phosphoric acid is dissolved in the dispersion liquid second dissolves, continue to stir 3.5 hours, obtain having the colloidal electrolyte of good thixotropic fluidity and gel stability.Do not add glass micro-fibers and Al
2O
3The contrast colloid viscosity of whisker is 1392mPa.s, adds glass micro-fibers and Al
2O
3The colloid viscosity of whisker is 236mPa.s.
By above-mentioned several embodiments as can be seen, Colliod electrolyte for accumulator provided by the invention has added the acicular nanometer whisker or the acicular nanometer fento of oxide, and its diameter is in nanometer range, and draw ratio is 5～20.Under stirring condition or under the field of flow effect, the acicular particles of this yardstick can be orientated fast along external force, reduces the internal friction resistance that colloid flows, and reduces the colloid kinematic viscosity.If the draw ratio of acicular particles is too little, as less than 5, be similar to spheroidal particle, the speed that is orientated along external force slows down, and interparticle frictional force increases, and colloid viscosity can not realize effective reduction; If the draw ratio of acicular particles is too big, as greater than 20, have the long fento of big fragility or whisker under external force frangibility be broken into the inhomogenous small-particle of size, the ability that is orientated along external force weakens, these small-particles frictional force when mobile is bigger, and the viscosity of colloid goes up not down.Therefore it is extremely important for reducing the colloid kinematic viscosity to control the suitable draw ratio of acicular particles.The acicular particles that adds suitable yardstick, colloidal electrolyte just have better thixotropic fluidity.Because this colloidal electrolyte thixotropic fluidity is big, viscosity only is 1/5th to 1/10th of common colloidal electrolyte, has improved encapsulating speed greatly, and the back is mended the glue probability and greatly reduced.Great amount of hydroxy group is contained on oxide whisker or nanometer fento surface, with gelatinizing agent SiO
2The surface has identical one-tenth glue functional group, very easily form the stabilizing gel network by hydrogen bond in the aqueous solution, and gel network has more high strength.With the storage battery that colloidal electrolyte of the present invention is made, electrolyte has lower viscosity during owing to perfusion, helps dividing plate and pole plate and absorbs more acid solution, and battery capacity enlarges markedly, and prolong useful life.Colloidal electrolyte of the present invention can more effective minimizing active material in the battery cyclic process disengaging, the growth and the infiltration of lead dendritic crystal, reduced the possibility of battery micro-short circuit.
The above; only be the preferable embodiment of the present invention; though in different embodiments, used different materials or component to make the target Colliod electrolyte for accumulator; but these materials all are based on the different implementations under the general idea of the present invention; and protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection range of claims.
Claims (10)
1. a Colliod electrolyte for accumulator is characterized in that, described Colliod electrolyte for accumulator is made by containing silica gel agent, mobile improvement and gel reinforcing agent, compound additive and electrolyte.
2. Colliod electrolyte for accumulator according to claim 1 is characterized in that, contains SiO in the silica gel agent described
2Specific area be 100～400m
2/ g, SiO in described colloidal electrolyte
2Weight ratio be 2.9～14.9%.
3. Colliod electrolyte for accumulator according to claim 1, it is characterized in that, described mobile improvement and gel reinforcing agent are the acicular nanometer whisker or the acicular nanometer fento of oxide, and the acicular nanometer whisker of described oxide or acicular nanometer fento are by MgO whisker, ZnO whisker, TiO
2Whisker, Al2O
3Any one or a few mixture is made in whisker or the glass micro-fibers.
4. Colliod electrolyte for accumulator according to claim 3 is characterized in that, the trans D of described acicular nanometer whisker or acicular nanometer fento is 10～50nm, and longitudinal length is 50～800nm, and draw ratio is 5～20 times.
5. Colliod electrolyte for accumulator according to claim 3 is characterized in that, in described mobile improvement and gel reinforcing agent, the composition of flow improving agent accounts for 0.05～1% weight portion of colloid amount in the colloidal electrolyte.
6. Colliod electrolyte for accumulator according to claim 1, it is characterized in that, described compound additive comprises the polyalcohol of 1～3% weight portion that accounts for the colloid amount, the cobaltous sulfate of 0.01～0.5% weight portion, the phosphoric acid of 3～5% weight portion sodium sulphate and 4.5～6.5% weight portions.
7. Colliod electrolyte for accumulator according to claim 6 is characterized in that, described polyalcohol is any one or a few the mixture in ethylene glycol, glycerol, pentaerythrite, sucrose or the starch.
8. Colliod electrolyte for accumulator according to claim 1 is characterized in that, described electrolyte is dilute sulfuric acid.
9. Colliod electrolyte for accumulator according to claim 8 is characterized in that, described dilute sulfuric acid concentration is 35～45%.
10. the preparation method of a Colliod electrolyte for accumulator is characterized in that, this method comprises:
Step 1 will contain silica gel agent and be distributed to that to make concentration in 35～45% the sulfuric acid solution be 2.9～14.9% colloidal dispersion, 50 ℃ of following strong agitation 2～8 hours, obtain the dispersion liquid first;
Step 2, to be distributed in the affiliated colloidal dispersion first by mobile improvement and the gel reinforcing agent that acicular nanometer whisker or acicular nanometer fento are made, and adjust the amount of flow ability modifying agent in described mobile improvement and the gel reinforcing agent, make the amount of described flow ability modifying agent account for 0.05～1% weight portion of colloid amount, dispersed with stirring was reduced to room temperature after 4～8 hours, obtained dispersion liquid second;
Step 3 is dissolved into compound additive in the described dispersion liquid second, regulates described compound additive and consists of 8.5～15% weight portions that account for the colloid amount, stirs 1～4 hour, obtains the target Colliod electrolyte for accumulator.
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| CN2010105270155A CN102005613A (en) | 2010-10-26 | 2010-10-26 | Colloid electrolyte of storage battery and preparation method thereof |
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| CN2010105270155A CN102005613A (en) | 2010-10-26 | 2010-10-26 | Colloid electrolyte of storage battery and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102044711A (en) * | 2010-12-08 | 2011-05-04 | 华南师范大学 | Storage battery colloidal electrolyte containing acicular nano crystal whisker and preparation method thereof |
| CN103199306A (en) * | 2013-03-08 | 2013-07-10 | 超威电源有限公司 | Colloid electrolyte formula for traction battery |
| CN107275674A (en) * | 2017-05-23 | 2017-10-20 | 天能电池(芜湖)有限公司 | A kind of combined electrolysis solution additive |
| CN107910605A (en) * | 2017-10-27 | 2018-04-13 | 竹开龙 | A kind of electrolyte and the nano-silicon alloy cell comprising the electrolyte |
| TWI641171B (en) * | 2018-02-13 | 2018-11-11 | 吳高翔 | Superconducting nano battery |
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| CN1056019A (en) * | 1990-04-26 | 1991-11-06 | 王莲香 | Colloid electrolyte of high electric capacity and method for making |
| CN101246968A (en) * | 2007-07-30 | 2008-08-20 | 华南师范大学 | Nano-gas-phase SiO2 colloid electrolytic solution and its preparing method and colloid accumulator |
| CN101291002A (en) * | 2008-05-06 | 2008-10-22 | 浙江超威电源有限公司 | Colloidal electrolyte of lead acid batteries |
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| CN1056019A (en) * | 1990-04-26 | 1991-11-06 | 王莲香 | Colloid electrolyte of high electric capacity and method for making |
| CN101246968A (en) * | 2007-07-30 | 2008-08-20 | 华南师范大学 | Nano-gas-phase SiO2 colloid electrolytic solution and its preparing method and colloid accumulator |
| CN101291002A (en) * | 2008-05-06 | 2008-10-22 | 浙江超威电源有限公司 | Colloidal electrolyte of lead acid batteries |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102044711A (en) * | 2010-12-08 | 2011-05-04 | 华南师范大学 | Storage battery colloidal electrolyte containing acicular nano crystal whisker and preparation method thereof |
| CN102044711B (en) * | 2010-12-08 | 2013-07-17 | 华南师范大学 | Storage battery colloidal electrolyte containing acicular nano crystal whisker and preparation method thereof |
| CN103199306A (en) * | 2013-03-08 | 2013-07-10 | 超威电源有限公司 | Colloid electrolyte formula for traction battery |
| CN103199306B (en) * | 2013-03-08 | 2015-12-02 | 超威电源有限公司 | Traction-type cell colloidal electrolyte formula |
| CN107275674A (en) * | 2017-05-23 | 2017-10-20 | 天能电池(芜湖)有限公司 | A kind of combined electrolysis solution additive |
| CN107910605A (en) * | 2017-10-27 | 2018-04-13 | 竹开龙 | A kind of electrolyte and the nano-silicon alloy cell comprising the electrolyte |
| TWI641171B (en) * | 2018-02-13 | 2018-11-11 | 吳高翔 | Superconducting nano battery |
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Application publication date: 20110406 |