CN1505186A - Lead-acid storage battery having added nano carbonaceous material and method for making same - Google Patents
Lead-acid storage battery having added nano carbonaceous material and method for making same Download PDFInfo
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- CN1505186A CN1505186A CNA021446806A CN02144680A CN1505186A CN 1505186 A CN1505186 A CN 1505186A CN A021446806 A CNA021446806 A CN A021446806A CN 02144680 A CN02144680 A CN 02144680A CN 1505186 A CN1505186 A CN 1505186A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 67
- 239000002253 acid Substances 0.000 title claims abstract description 38
- 238000003860 storage Methods 0.000 title claims description 5
- 238000000034 method Methods 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 22
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 238000005087 graphitization Methods 0.000 claims description 14
- 239000002041 carbon nanotube Substances 0.000 claims description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 12
- 229920005610 lignin Polymers 0.000 claims description 10
- 239000011505 plaster Substances 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 20
- 239000011149 active material Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 239000006230 acetylene black Substances 0.000 description 12
- 239000013543 active substance Substances 0.000 description 12
- 239000006071 cream Substances 0.000 description 12
- 238000007599 discharging Methods 0.000 description 12
- 238000009472 formulation Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 5
- 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
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- 238000005670 sulfation reaction 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 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
- 238000005520 cutting process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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 provides a plumbous acid accumulator which contains nano carbonaceous material in its positive or/and negative polar plate and its making method. The nano carbonaceous material can be unidimensional and has 1nm-200nm diameter and 100nm-20 mu m length.
Description
Technical field
Patented technology provided by the invention belongs to lead acid accumulator and preparation method thereof.
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 a kind of at positive plate or/and contain the lead acid accumulator of nanometer carbon material in the negative plate.
Nanometer carbon material can be an one dimension.The diameter of nanometer carbon material is 1nm～200nm, and length is 100nm～20 μ m.
The 1-dimention nano carbonaceous material is added in the polar plate of lead acid storage battery, improved the active material utilization of lead acid accumulator, improved the charge acceptance of lead acid accumulator, improved the pole plate formation efficiency.
The present invention also provides the preparation method of the lead acid accumulator that contains nanometer carbon material.
The preparation method who contains the positive plate of nanometer carbon material in this lead acid accumulator: can be that CNT (carbon nano-tube) is carried out preliminary treatment, promptly carry out purification processes and cut processing with weak point, obtain 1-dimention nano carbonaceous material diameter between 1nm～200nm, length is between 100nm～20 μ m, draw ratio is 50～5000, adds in the lead plaster to make positive plate; Also can be that (1) will handle back 1-dimention nano carbonaceous material and dispersant, the ratio of 1-dimention nano carbonaceous material and dispersant be to boil 1～20 hour in 100: 10～100: 60, heats aforesaid liquid under 100～250 ℃ of conditions, is made into paste; (2) grind this paste: thin up, paste and water ratio are 1: 1～1: 100, and shear and disperse, and obtain stable dispersions; (3) will make positive plate in this dispersion liquid adding lead plaster.
Wherein dispersant is neopelex, polyvinyl alcohol or CMC.
Wherein through pretreated nanometer carbon material again under 2000～3000 ℃ of high temperature, be preferably 2200～2600 ℃ of following graphitization processing, and then and dispersant.
The preparation method who contains the negative plate of nanometer carbon material in this lead acid accumulator: can be that CNT (carbon nano-tube) is carried out preliminary treatment, promptly carry out purification processes and cut processing with weak point, obtain 1-dimention nano carbonaceous material diameter between 1nm～200nm, length is between 100nm～20 μ m, and draw ratio is 50～5000; Add in lead powder, sulfuric acid, water, lignin and the barium sulfate and make negative plate.Also can be that (1) will handle back 1-dimention nano carbonaceous material and dispersant, the 1-dimention nano carbonaceous material be 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; (2) grind this paste: thin up, paste and water ratio are 1: 1～1: 100, and shear and disperse, and obtain stable dispersions; (34) will make negative plate in this dispersion liquid adding lead powder, sulfuric acid, water, lignin and the barium sulfate.
Wherein dispersant is neopelex, polyvinyl alcohol or CMC.
Wherein through pretreated nanometer carbon material again under 2000～3000 ℃ of high temperature, be preferably under 2200～2600 ℃ graphitization processing, and then and dispersant.
Description of drawings
Fig. 1 has or not the active substance for positive electrode of lead-acid accumulator utilance of 1/10th 100nm 1-dimention nano carbonaceous materials and the relation between the discharge stream
Fig. 2 has or not the lead-acid battery negative pole active substance utilance of 1/10th 100nm 1-dimention nano carbonaceous materials and the relation between the discharge stream
Fig. 3 has or not the active substance for positive electrode of lead-acid accumulator utilance of 1/10th 50nm 1-dimention nano carbonaceous materials and the relation between the discharge stream
Fig. 4 has or not the lead-acid battery negative pole active substance utilance of 1/10th 50nm 1-dimention nano carbonaceous materials and the relation between the discharge stream
Fig. 5 has or not the active substance for positive electrode of lead-acid accumulator utilance of 1/10th graphitization 100nm 1-dimention nano carbonaceous materials and the relation between the discharge stream
Fig. 6 has or not the lead-acid battery negative pole active substance utilance of 1/10th graphitization 100nm 1-dimention nano carbonaceous materials and the relation between the discharge stream
Fig. 7 has or not the active substance for positive electrode of lead-acid accumulator utilance of 1/10th graphitization 50nm 1-dimention nano carbonaceous materials and the relation between the discharge stream
Fig. 8 has or not the lead-acid battery negative pole active substance utilance of 1/10th graphitization 50nm 1-dimention nano carbonaceous materials and the relation between the discharge stream
Fig. 9 has or not the active substance for positive electrode of lead-acid accumulator utilance of 1/10th 100nm 1-dimention nano carbonaceous material dispersion liquids and the relation between the discharge stream
Figure 10 has or not the lead-acid battery negative pole active substance utilance of 1/10th 100nm 1-dimention nano carbonaceous material dispersion liquids and the relation between the discharge stream
Figure 11 has or not the active substance for positive electrode of lead-acid accumulator utilance of 1/10th 50nm 1-dimention nano carbonaceous material dispersion liquids and the relation between the discharge stream
Figure 12 has or not the lead-acid battery negative pole active substance utilance of 1/10th 50nm 1-dimention nano carbonaceous material dispersion liquids and the relation between the discharge stream.
Embodiment
Below in conjunction with being that embodiment and comparative example describe the present invention in detail.
Get 1 gram pretreated (promptly carry out purification processes and short cutting handled) 1-dimention nano carbonaceous material (average diameter 100nm), restrain lead powder and mix, after mixing by general standard anode diachylon preparation method, be coated with cream and obtain positive plate with 10.Negative plate is by the general standard formulation, and main component has lead powder, sulfuric acid, water, lignin, barium sulfate and acetylene black.30 ℃, solidify after 24 hours under humidity 100% condition, be combined into cell with two negative plates and a slice positive plate.After changing into, measure the discharge capacity under the different discharging currents, calculate the positive plate active material utilization.The results are shown in Figure 1, curve a.As can be seen from the figure, add the 1-dimention nano material with carbon element and can effectively improve positive electrode active material utilization.
Comparative example 1
Do not add the 1-dimention nano carbonaceous material and the results are shown in Figure 1, curve b.
Get the pretreated 1-dimention nano carbonaceous material (average diameter 100nm) of 1 gram, mix with 10 gram lead powder.Then, prepare cathode lead plaster, obtain negative plate after being coated with cream by cathode formula in the example 1 (not comprising acetylene black) and method.Positive plate is by the general standard formulation.30 ℃, solidify after 24 hours under humidity 100% condition, be combined into cell with two positive plates and a slice negative plate.After changing into, measure the discharge capacity under the different discharging currents, calculate the positive and negative pole active matter utilance.The results are shown in Figure 2, curve a.As can be seen from the figure, add the 1-dimention nano material with carbon element and can effectively improve the negative electrode active material utilance.
Comparative example 2
Do not add the 1-dimention nano carbonaceous material and the results are shown in Figure 2, curve b.
Embodiment 3
Get the pretreated 1-dimention nano carbonaceous material (average diameter 50nm) of 1 gram, mix, after mixing by general standard anode diachylon preparation method, be coated with cream and obtain positive plate with 10 gram lead powder.Negative plate is by the general standard formulation, and main component has lead powder, sulfuric acid, water, lignin, barium sulfate and acetylene black.30 ℃, solidify after 24 hours under humidity 100% condition, be combined into cell with two negative plates and a slice positive plate.After changing into, measure the discharge capacity under the different discharging currents, calculate the positive plate active material utilization.The results are shown in Figure 3, curve a.
Comparative example 3
Do not add the 1-dimention nano carbonaceous material and the results are shown in Figure 3, curve b.
Embodiment 4
Get the pretreated 1-dimention nano carbonaceous material (average diameter 50nm) of 1 gram, mix with 10 gram lead powder.Then, prepare cathode lead plaster, obtain negative plate after being coated with cream by cathode formula in the example 1 (not comprising acetylene black) and method.Positive plate is by the general standard formulation.30 ℃, solidify after 24 hours under humidity 100% condition, be combined into cell with two positive plates and a slice negative plate.After changing into, measure the discharge capacity under the different discharging currents, calculate the positive and negative pole active matter utilance.The results are shown in Figure 4, curve a.
Comparative example 4
Do not add the 1-dimention nano carbonaceous material and the results are shown in Figure 4, curve b
Embodiment 5
After getting 1 gram preliminary treatment, the 1-dimention nano carbonaceous material (average diameter 100nm) in that 2400 ℃ of graphitizations are crossed mixes with 10 gram lead powder, after mixing by general standard anode diachylon preparation method, is coated with cream and obtains positive plate.Negative plate is by the general standard formulation, and main component has lead powder, sulfuric acid, water, lignin, barium sulfate and acetylene black.30 ℃, solidify after 24 hours under humidity 100% condition, be combined into cell with two negative plates and a slice positive plate.After changing into, measure the discharge capacity under the different discharging currents, calculate the positive plate active material utilization.The results are shown in Figure 5, curve a.
Comparative example 5
Do not add the 1-dimention nano carbonaceous material and the results are shown in Figure 5, curve b.
Embodiment 6
After getting 1 gram preliminary treatment, the 1-dimention nano carbonaceous material (average diameter 100nm) in that 2400 ℃ of graphitizations are crossed mixes with 10 gram lead powder.Then, prepare cathode lead plaster, obtain negative plate after being coated with cream by cathode formula in the example 1 (not comprising acetylene black) and method.Positive plate is by the general standard formulation.30 ℃, solidify after 24 hours under humidity 100% condition, be combined into cell with two positive plates and a slice negative plate.After changing into, measure the discharge capacity under the different discharging currents, calculate the positive and negative pole active matter utilance.The results are shown in Figure 6, curve a.
Comparative example 6
Do not add the 1-dimention nano carbonaceous material and the results are shown in Figure 6, curve b
Embodiment 7
After getting 1 gram preliminary treatment, the 1-dimention nano carbonaceous material (average diameter 50nm) in that 2400 ℃ of graphitizations are crossed mixes with 10 gram lead powder, after mixing by general standard anode diachylon preparation method, is coated with cream and obtains positive plate.Negative plate is by the general standard formulation, and main component has lead powder, sulfuric acid, water, lignin, barium sulfate and acetylene black.30 ℃, solidify after 24 hours under humidity 100% condition, be combined into cell with two negative plates and a slice positive plate.After changing into, measure the discharge capacity under the different discharging currents, calculate the positive plate active material utilization.The results are shown in Figure 7, curve a.
Comparative example 7
Do not add the 1-dimention nano carbonaceous material and the results are shown in Figure 7, curve b.
Embodiment 8
After getting 1 gram preliminary treatment, the 1-dimention nano carbonaceous material (average diameter 50nm) in that 2400 ℃ of graphitizations are crossed mixes with 10 gram lead powder.Then, prepare cathode lead plaster, obtain negative plate after being coated with cream by cathode formula in the example 1 (not comprising acetylene black) and method.Positive plate is by the general standard formulation.30 ℃, solidify after 24 hours under humidity 100% condition, be combined into cell with two positive plates and a slice negative plate.After changing into, measure the discharge capacity under the different discharging currents, calculate the positive and negative pole active matter utilance.The results are shown in Figure 8, curve a.
Comparative example 8
Do not add the 1-dimention nano carbonaceous material and the results are shown in Figure 8, curve b
Embodiment 9:
After getting 5 gram preliminary treatment,, add 2.5 gram dispersants and 100 gram water, boiled 2 hours at the 1-dimention nano carbonaceous material (average diameter 100nm) 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 the such dispersion liquid of 1 gram, mix, after mixing by general standard anode diachylon preparation method, be coated with cream and obtain positive plate with 10 gram lead powder.Negative plate is by the general standard formulation, and main component has lead powder, sulfuric acid, water, lignin, barium sulfate and acetylene black.30 ℃, solidify after 24 hours under humidity 100% condition, be combined into cell with two negative plates and a slice positive plate.After changing into, measure the discharge capacity under the different discharging currents, calculate the positive plate active material utilization.The results are shown in Figure 9, curve a.
Comparative example 9
Do not add the 1-dimention nano carbonaceous material and the results are shown in Figure 9, curve b.
Get 1 gram and embodiment 9 identical dispersion liquids, mix with 10 gram lead powder.Then, prepare cathode lead plaster, obtain negative plate after being coated with cream by cathode formula in the example 1 (not comprising acetylene black) and method.Positive plate is by the general standard formulation.30 ℃, solidify after 24 hours under humidity 100% condition, be combined into cell with two positive plates and a slice negative plate.After changing into, measure the discharge capacity under the different discharging currents, calculate the positive and negative pole active matter utilance.The results are shown in Figure 10, curve a.
Comparative example 10
Do not add the 1-dimention nano carbonaceous material and the results are shown in Figure 10, curve b
Embodiment 11:
After getting 5 gram preliminary treatment,, 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.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 the such dispersion liquid of 1 gram, mix, after mixing by general standard anode diachylon preparation method, be coated with cream and obtain positive plate with 10 gram lead powder.Negative plate is by the general standard formulation, and main component has lead powder, sulfuric acid, water, lignin, barium sulfate and acetylene black.30 ℃, solidify after 24 hours under humidity 100% condition, be combined into cell with two negative plates and a slice positive plate.After changing into, measure the discharge capacity under the different discharging currents, calculate the positive plate active material utilization.The results are shown in Figure 11, curve a.
Comparative example 11
Do not add the 1-dimention nano carbonaceous material and the results are shown in Figure 11, curve b.
Embodiment 12
Get 1 gram and embodiment 11 identical dispersion liquids, mix with 10 gram lead powder.Then, prepare cathode lead plaster, obtain negative plate after being coated with cream by cathode formula in the example 1 (not comprising acetylene black) and method.Positive plate is by the general standard formulation.30 ℃, solidify after 24 hours under humidity 100% condition, be combined into cell with two positive plates and a slice negative plate.After changing into, measure the discharge capacity under the different discharging currents, calculate the positive and negative pole active matter utilance.The results are shown in Figure 12, curve a.
Comparative example 12
Do not add the 1-dimention nano carbonaceous material and the results are shown in Figure 12, curve b.
Claims (8)
1 one kinds of lead acid accumulators is characterized in that positive pole in the storage battery or/and negative plate contains nanometer carbon material.
2 according to the described lead acid accumulator 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 draw ratio is 50～5000.
The preparation method of the described lead acid accumulator of 3 claims 1, it is characterized in that: wherein the preparation method of positive plate is as follows: CNT (carbon nano-tube) is carried out preliminary treatment: promptly purification processes and weak point are cut processing, obtain 1-dimention nano carbonaceous material diameter between 1nm～200nm, length is between 100nm～20 μ m, draw ratio is 50～5000, adds in the lead plaster with suitable ratio and makes positive plate.
4 preparation methods according to the described lead acid accumulator of claim 3 is characterized in that:
(1) will handle back 1-dimention nano carbonaceous material and dispersant, the ratio of 1-dimention nano carbonaceous material and dispersant is to boil 1～20 hour in 100: 10～100: 60, heats aforesaid liquid under 100～250 ℃ of conditions, is made into paste;
(2) grind this paste: thin up, paste and water ratio are 1: 1～1: 100, and shear and disperse, and obtain stable dispersions.
(3) will make positive plate in this dispersion liquid adding lead plaster.
The preparation method of the described lead acid accumulator of 5 claims 1, it is characterized in that: wherein the preparation method of negative plate is as follows: CNT (carbon nano-tube) is carried out preliminary treatment: promptly purification processes and weak point are cut processing, obtain 1-dimention nano carbonaceous material diameter between 1nm～200nm, length is between 100nm～20 μ m, draw ratio is 50～5000, adds in lead powder, sulfuric acid, water, lignin and the barium sulfate to make negative plate.
6 according to the described preparation method of claim 5, it is characterized in that:
(1) 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;
(2) grind this paste: thin up, paste and water ratio are 1: 1～1: 100, and shear and disperse, and obtain stable dispersions;
(3) will make negative plate in this dispersion liquid adding lead powder, sulfuric acid, water, lignin and the barium sulfate.
7 preparation methods according to claim 4 or 6 described lead acid accumulators is characterized in that dispersant is neopelex, polyvinyl alcohol or CMC.
8 preparation methods according to the described lead acid accumulator of claim 7 is characterized in that through pretreated nanometer carbon material again in 2000～3000 ℃ of following graphitization processing of high temperature, and then and dispersant.
9 preparation methods according to the described lead acid accumulator of claim 8, the temperature that it is characterized in that graphitization processing is 2200～2600 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021446806A CN1230929C (en) | 2002-12-04 | 2002-12-04 | Lead-acid storage battery having added nano carbonaceous material and method for making same |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021446806A CN1230929C (en) | 2002-12-04 | 2002-12-04 | Lead-acid storage battery having added nano carbonaceous material and method for making same |
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| CN1505186A true CN1505186A (en) | 2004-06-16 |
| CN1230929C CN1230929C (en) | 2005-12-07 |
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| CN100367558C (en) * | 2005-12-22 | 2008-02-06 | 上海交通大学 | Method for lengthening hermetic lead accumulator operation life |
| 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 |
| CN100409471C (en) * | 2005-04-13 | 2008-08-06 | 北京天中树科技发展有限公司 | Nano-lead-acid accumulator battery electrode plate |
| CN103765642A (en) * | 2011-06-23 | 2014-04-30 | 分子钢筋设计有限责任公司 | Lead-acid battery formulations containing discrete carbon nanotubes |
| DE102015205726A1 (en) | 2014-03-31 | 2015-10-01 | Eternal Materials Co., Ltd. | electrolyte composition |
| CN105161770A (en) * | 2015-08-18 | 2015-12-16 | 超威电源有限公司 | Lead plaster additive for lead-acid storage battery, and preparation method and application therefor |
| CN106410190A (en) * | 2016-11-16 | 2017-02-15 | 双登集团股份有限公司 | Lead-acid storage battery positive lead paste preparation method |
| CN107732250A (en) * | 2017-08-30 | 2018-02-23 | 淄博火炬能源有限责任公司 | Charge type battery and preparation method thereof |
| CN112635761A (en) * | 2019-09-24 | 2021-04-09 | 广隆光电科技股份有限公司 | Negative electrode lead paste composition of lead-acid battery, negative plate and lead-acid battery |
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2002
- 2002-12-04 CN CNB021446806A patent/CN1230929C/en not_active Expired - Fee Related
Cited By (11)
| 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 |
| CN100409471C (en) * | 2005-04-13 | 2008-08-06 | 北京天中树科技发展有限公司 | Nano-lead-acid accumulator battery electrode plate |
| CN100367558C (en) * | 2005-12-22 | 2008-02-06 | 上海交通大学 | Method for lengthening hermetic lead accumulator operation life |
| CN103765642A (en) * | 2011-06-23 | 2014-04-30 | 分子钢筋设计有限责任公司 | Lead-acid battery formulations containing discrete carbon nanotubes |
| CN103765642B (en) * | 2011-06-23 | 2016-07-06 | 分子钢筋设计有限责任公司 | Comprise the lead-acid battery preparation of discrete CNT |
| DE102015205726A1 (en) | 2014-03-31 | 2015-10-01 | Eternal Materials Co., Ltd. | electrolyte composition |
| US9735449B2 (en) | 2014-03-31 | 2017-08-15 | Eternal Materials Co., Ltd. | Electrolyte composition |
| CN105161770A (en) * | 2015-08-18 | 2015-12-16 | 超威电源有限公司 | Lead plaster additive for lead-acid storage battery, and preparation method and application therefor |
| CN106410190A (en) * | 2016-11-16 | 2017-02-15 | 双登集团股份有限公司 | Lead-acid storage battery positive lead paste preparation method |
| CN107732250A (en) * | 2017-08-30 | 2018-02-23 | 淄博火炬能源有限责任公司 | Charge type battery and preparation method thereof |
| CN112635761A (en) * | 2019-09-24 | 2021-04-09 | 广隆光电科技股份有限公司 | Negative electrode lead paste composition of lead-acid battery, negative plate and lead-acid battery |
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