CN1505191A - Addition agent for lead-acid storage battery and method for making same - Google Patents
Addition agent for lead-acid storage battery and method for making same Download PDFInfo
- Publication number
- CN1505191A CN1505191A CNA021446814A CN02144681A CN1505191A CN 1505191 A CN1505191 A CN 1505191A CN A021446814 A CNA021446814 A CN A021446814A CN 02144681 A CN02144681 A CN 02144681A CN 1505191 A CN1505191 A CN 1505191A
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- Prior art keywords
- dispersant
- acid accumulator
- paste
- carbonaceous material
- carbon material
- Prior art date
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- 239000002253 acid Substances 0.000 title claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 title 1
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 32
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- 238000005087 graphitization Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 3
- 239000002000 Electrolyte additive Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 239000013543 active substance Substances 0.000 abstract 1
- 229910021392 nanocarbon Inorganic materials 0.000 abstract 1
- 239000011149 active material Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000019635 sulfation Effects 0.000 description 3
- 238000005670 sulfation reaction Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an additive made by adding water to nano carbon material and dispersant. The ratio of the former to the latter is 100 : 10-60. It adds one-dimensional carbon material to the electrolyte of the plumbous acid accumulator, to heighten utilization ratio of active substance and charge endurance of the plumbous acid accumulator
Description
Technical field
Patented technology provided by the invention belongs to additive and preparation method thereof, is applicable to lead acid accumulator.
Background technology
Over more than 100 year, lead acid accumulator is because of its low price, and raw material is easy to get, the advantage of dependable performance, always in secondary battery industry in occupation of critical role.But, in the last few years,, further improved specific energy of lead acid battery along with the appearance of batteries such as Ni-MH battery, lithium ion battery, prolong its useful life, be its unique channel that still can in Battery Market, occupy a tiny space from now on.Usually improve the active material utilization of lead acid accumulator, tend to the negative effect that brings the life of storage battery to reduce.Because in order to improve active material utilization, the volume or the concentration that need to reduce the active material consumption or increase electrolyte (sulfuric acid), for the certain lead acid accumulator of volume and weight, softening and the possibility that comes off take place in this inevitable active material that strengthen greatly.Simultaneously, high-concentration sulfuric acid quickens negative plate generation sulfation toward the contact meeting, and these all can make the lost of life of lead acid accumulator.By being effectively to improve active material utilization, can avoid occurring a kind of good means of harmful effect to the inner interpolation of pole plate conductive materials.Characteristics such as that the raw material of wood-charcoal material has is in light weight, good electrical conductivity good, strong corrosion resistant and mechanical property excellence become the preferred material of pole plate conductive additive, add in the polar plate of lead acid storage battery, can improve active material utilization, part suppresses sulfation and prevents active material obscission generation etc.But, the raw material of wood-charcoal material of Shi Yonging in the past, as graphite powder, carbon fiber and carbon black, there is big, the dispersed relatively poor shortcoming between active material of particle diameter mostly, addition can't form good three-dimensional conductive network more after a little while in active material, be difficult to realize improving the useful life of active material utilization, raising battery, so effect is very limited.
Summary of the invention
Lead acid accumulator adopts the 1-dimention nano carbonaceous material as adding material, and the 1-dimention nano carbonaceous material is meant the fibrous carbonaceous material of diameter below 200 nanometers, comprises CNT (carbon nano-tube) and carbon nano-fiber.Compare with traditional carbon fiber, the 1-dimention nano carbonaceous material has the particular structure feature, structure, draw ratio as nanoscale is big, fault of construction is few, specific area is big etc., this makes the 1-dimention nano carbonaceous material except the advantage with general raw material of wood-charcoal material, also overcome its shortcoming simultaneously, shown excellent more mechanics, electricity and chemical property.
The invention provides and a kind ofly add the additive that water is formed by nanometer carbon material and dispersant.Nanometer carbon material is 100: 10～100: 60 with the ratio of dispersant.
Nanometer carbon material can be an one dimension.The diameter of nanometer carbon material is 1nm～200nm, and length is 100nm～20 μ m.Dispersant can be neopelex, polyvinyl alcohol or CMC.
The 1-dimention nano carbonaceous material is added in the lead-acid accumulator electrolyte,, improve the charge acceptance of lead acid accumulator to improve the active material utilization of lead acid accumulator.
The present invention also provides the preparation method of this additive:
(1) preliminary treatment of CNT (carbon nano-tube): promptly carry out purification processes and cut processing with short, obtain 1-dimention nano carbonaceous material diameter between 1nm～200nm, length is between 100nm～20 μ m, and draw ratio is 50～5000;
(2) will handle back 1-dimention nano carbonaceous material and dispersant: the 1-dimention nano carbonaceous material is 100: 10～100: 60 with the ratio of dispersant, boils 1～20 hour, heats aforesaid liquid under 100～250 ℃ of conditions, is made into paste;
(3) grind this paste: thin up, paste and water ratio are 1: 1～1: 100, and shear and disperse, and obtain stable dispersions, i.e. the lead-acid accumulator electrolyte additive.
First under 2000～3000 ℃ of high temperature through pretreated nanometer carbon material, be preferably under 2200～2600 ℃ graphitization processing, and then and dispersant.
Description of drawings
Fig. 1 lead acid accumulator adds the useful life before and after the 1-dimention nano carbonaceous material dispersion liquid.
Discharge curve before and after Fig. 2 lead acid accumulator (model 6N4) activates with 1-dimention nano carbonaceous material dispersion liquid.
Embodiment
After getting 5 gram preliminary treatment,, add 1 gram dispersant and 100 gram water, boiled 2 hours at the 1-dimention nano carbonaceous material (average diameter 50nm) that 2400 ℃ of graphitizations are crossed.Then, dispersion liquid 150 ℃ of heating down, is made into paste.To change paste and put into ball mill, ball milling 2 hours.Then, add 200 gram water dilutions, high shear obtained the stable carbon nanotube dispersion liquid after 20 minutes.Get 9 milliliters of above-mentioned dispersion liquids, after mixing with 80 milliliters of electrolyte, join in the 6N4 motorcycle battery, carry out the rated capacity test.The system of discharging and recharging is that 0.4A charges to 8.4V, and 0.4A is discharged to 5.75V, circulates three times.Recording its rated capacity is 4.2Ah, and the capacity that does not add the storage battery of dispersion liquid is 3.9Ah.And the primary charging time obviously shortens.Illustrate that the active material utilization that adds the lead acid accumulator behind the 1-dimention nano carbonaceous material dispersion liquid increases, and improved charge efficiency.
Embodiment 2
After getting 5 gram preliminary treatment,, add 1 gram dispersant and 100 gram water, boiled 2 hours at the 1-dimention nano carbonaceous material (average diameter 50nm) that 2400 ℃ of graphitizations are crossed.Then, dispersion liquid 150 ℃ of heating down, is made into paste.To change paste and put into ball mill, ball milling 2 hours.Then, add 200 gram water dilutions, high shear obtained the stable carbon nanotube dispersion liquid after 20 minutes.Get 9 milliliters of above-mentioned dispersion liquids, after mixing with 80 milliliters of electrolyte, join in the 6N4 motorcycle battery, carry out the charge and discharge cycles experiment.The system that discharges and recharges is as follows: 1A charging 4 hours, 4A is discharged to 3V.The result as shown in Figure 1a.Therefrom add the useful life that 1-dimention nano carbonaceous material dispersion liquid can improve lead acid accumulator as can be seen.
Comparative example 2
The result who does not add 1-dimention nano carbonaceous material dispersion liquid is shown in 1b.
Embodiment 3
After getting 5 gram preliminary treatment,, add 2 gram dispersants and 100 gram water, boiled 2 hours at the 1-dimention nano carbonaceous material (average diameter 50nm) that 2400 ℃ of graphitizations are crossed.Then, dispersion liquid 150 ℃ of heating down, is made into paste.To change paste and put into ball mill, ball milling 2 hours.Then, add 200 gram water dilutions, high shear obtained the stable carbon nanotube dispersion liquid after 20 minutes.Get in the 6-QA-60 lead acid accumulator that 100 milliliters of above-mentioned dispersion liquids join sulfation, carried out cycle charge-discharge 1 month then.The density of the electrolyte of lead acid accumulator is by initial 1.20g/cm
3, increase to 1.29g/cm
3Capacity restoration is to 58Ah.
Embodiment 4
After getting 5 gram preliminary treatment (promptly carry out purification processes and cut processing),, add 2.5 gram dispersants and 100 gram water, boiled 2 hours at the 1-dimention nano carbonaceous material (average diameter 50nm) that 2400 ℃ of graphitizations are crossed with weak point.Then, dispersion liquid 150 ℃ of heating down, is made into paste.To change paste and put into ball mill, ball milling 2 hours.Then, add 200 gram water dilutions, high shear obtained the stable carbon nanotube dispersion liquid after 20 minutes.
The lead acid accumulator of taking (model 6N4), with 0.4A current charges 10 hours, with the 4A current discharge to 3V, its discharge curve is shown in curve a among Fig. 2.Then, pour out 10% of former electrolyte volume, add the stable carbon nanotube dispersion liquid of respective amount, with 0.4A charging 10 hours, to 3V, its discharge curve was shown in curve b among Fig. 2 with the 4A current discharge again.
Claims (5)
1 one kinds of lead acid accumulator additives is characterized in that it adds water by nanometer carbon material and dispersant and forms, and nanometer carbon material is 100: 10～100: 60 with the ratio of dispersant.
2 according to the described additive of claim 1, it is characterized in that nanometer carbon material is an one dimension, and diameter is 1nm～200nm, and length is 100nm～20 μ m, and dispersant is neopelex, polyvinyl alcohol or CMC.
The preparation method of 3 claims 1 or 2 described additives is characterized in that:
(1) preliminary treatment of CNT (carbon nano-tube): promptly carry out purification processes and cut processing with short, obtain 1-dimention nano carbonaceous material diameter between 1nm～200nm, length is between 100nm～20 μ m, and draw ratio is 50～5000;
(2) will handle back 1-dimention nano carbonaceous material and dispersant, the 1-dimention nano carbonaceous material is 100: 10～100: 60 with the ratio of dispersant, boils 1～20 hour, heats aforesaid liquid under 100～250 ℃ of conditions, is made into paste;
(3) grind this paste: thin up, paste and water ratio are 1: 1～1: 100, and shear and disperse, and obtain stable dispersions, i.e. the lead-acid accumulator electrolyte additive.
4 according to the described preparation method of claim 3, it is characterized in that through pretreated nanometer carbon material again in 2000～3000 ℃ of following graphitization processing of high temperature, and then and dispersant.
5 according to the described preparation method of claim 4, and the temperature that it is characterized in that graphitization processing is 2200～2600 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021446814A CN1219336C (en) | 2002-12-04 | 2002-12-04 | Addition agent for lead-acid storage battery and method for making same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021446814A CN1219336C (en) | 2002-12-04 | 2002-12-04 | Addition agent for lead-acid storage battery and method for making same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1505191A true CN1505191A (en) | 2004-06-16 |
| CN1219336C CN1219336C (en) | 2005-09-14 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021446814A Expired - Fee Related CN1219336C (en) | 2002-12-04 | 2002-12-04 | Addition agent for lead-acid storage battery and method for making same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1219336C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100375327C (en) * | 2005-04-13 | 2008-03-12 | 北京天中树科技发展有限公司 | Nano lead-acid accumulator battery |
| CN100483833C (en) * | 2004-10-25 | 2009-04-29 | 深圳理士奥电源技术有限公司 | Nanometer-level high composite electrolyte and its preparing method |
-
2002
- 2002-12-04 CN CNB021446814A patent/CN1219336C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100483833C (en) * | 2004-10-25 | 2009-04-29 | 深圳理士奥电源技术有限公司 | Nanometer-level high composite electrolyte and its preparing method |
| CN100375327C (en) * | 2005-04-13 | 2008-03-12 | 北京天中树科技发展有限公司 | Nano lead-acid accumulator battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1219336C (en) | 2005-09-14 |
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