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CN1230929C - 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 PDF

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CN1230929C
CN1230929C CNB021446806A CN02144680A CN1230929C CN 1230929 C CN1230929 C CN 1230929C CN B021446806 A CNB021446806 A CN B021446806A CN 02144680 A CN02144680 A CN 02144680A CN 1230929 C CN1230929 C CN 1230929C
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lead
paste
preparation
dispersant
water
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CN1505186A (en
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成会明
李洪锡
童昕
李峰
张国虎
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Institute of Metal Research of CAS
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    • Y02E60/10Energy storage using batteries

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Abstract

本发明提供一种在正极板或/和负极板中含有纳米碳质材料的铅酸蓄电池,及其制备方法。纳米碳质材料可以是一维的。纳米碳质材料的直径为1nm~200nm,长度为100nm~20μm。The invention provides a lead-acid accumulator containing nano-carbon materials in positive plates or/and negative plates, and a preparation method thereof. Nanocarbonaceous materials may be one-dimensional. The diameter of the nano carbonaceous material is 1 nm to 200 nm, and the length is 100 nm to 20 μm.

Description

Add lead acid accumulator of nanometer carbon material and preparation method thereof
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.
Embodiment 1
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.
Embodiment 2
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.
Embodiment 10
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 (6)

1 一种铅酸蓄电池,其特征在于蓄电池中正极或/和负极板含有一维纳米碳质材料,直径为1nm~200nm,长度为100nm~20μm,长径比为50~5000。1 A lead-acid battery, characterized in that the positive and/or negative plates in the battery contain one-dimensional nano-carbon materials, with a diameter of 1nm to 200nm, a length of 100nm to 20μm, and an aspect ratio of 50 to 5000. 2 权利要求1所述的铅酸蓄电池的制备方法,其特征在于:其中正极板的制备方法如下:2 the preparation method of lead-acid storage battery described in claim 1 is characterized in that: wherein the preparation method of positive plate is as follows: (1)纳米碳管进行预处理:即提纯处理和短切处理,得到一维纳米碳质材料直径介于1nm~200nm,长度介于100nm~20μm,长径比为50~5000,以合适的比例加入铅膏中制成正极板;(1) Pretreatment of carbon nanotubes: that is, purification treatment and chopping treatment to obtain one-dimensional carbon nanomaterials with a diameter ranging from 1nm to 200nm, a length ranging from 100nm to 20μm, and an aspect ratio of 50 to 5000. Proportionally added to the lead paste to make a positive plate; (2)将处理后一维纳米碳质材料与分散剂混合,一维纳米碳质材料与分散剂的比为100∶10~100∶60煮沸1~20小时,在100~250℃条件下加热上述液体,将其制成膏状物;(2) Mix the treated one-dimensional carbonaceous nanomaterial with a dispersant, the ratio of the one-dimensional carbonaceous nanomaterial to the dispersant is 100:10~100:60, boil for 1~20 hours, and heat at 100~250°C The above-mentioned liquid is made into a paste; (3)研磨该膏状物:加水稀释,膏状物与水比例为1∶1~1∶100,并剪切分散,得到稳定分散液;(3) Grinding the paste: dilute with water, the ratio of paste to water is 1:1 to 1:100, and shear and disperse to obtain a stable dispersion; (4)将此分散液加入铅膏中制成正极板。(4) Add this dispersion to lead paste to make a positive plate. 3 权利要求1所述的铅酸蓄电池的制备方法,其特征在于:其中负极板的制备方法如下:3 The preparation method of the lead-acid storage battery according to claim 1, characterized in that: wherein the preparation method of the negative plate is as follows: (1)纳米碳管进行预处理:即提纯处理和短切处理,得到一维纳米碳质材料直径介于1nm~200nm,长度介于100nm~20μm,长径比为50~5000,加入铅粉、硫酸、水、木素和硫酸钡中制成负极板;(1) Pretreatment of carbon nanotubes: that is, purification and chopping to obtain one-dimensional nanocarbon materials with a diameter of 1nm to 200nm, a length of 100nm to 20μm, and an aspect ratio of 50 to 5000. Add lead powder , sulfuric acid, water, lignin and barium sulfate to make negative plates; (2)将处理后一维纳米碳质材料与分散剂混合,一维纳米碳质材料与分散剂的比为100∶10~100∶60,煮沸1~20小时,在100~250℃条件下加热上述液体,将其制成膏状物;(2) Mix the treated one-dimensional carbonaceous nanomaterial with a dispersant, the ratio of the one-dimensional carbonaceous nanomaterial to the dispersant is 100:10 to 100:60, boil for 1 to 20 hours, at 100 to 250°C Heat the above liquid to make a paste; (3)研磨该膏状物:加水稀释,膏状物与水比例为1∶1~1∶100,并剪切分散,得到稳定分散液;(3) Grinding the paste: dilute with water, the ratio of paste to water is 1:1 to 1:100, and shear and disperse to obtain a stable dispersion; (4)将此分散液加入铅粉、硫酸、水、木素和硫酸钡中制成负极板。(4) Add the dispersion liquid to lead powder, sulfuric acid, water, lignin and barium sulfate to make a negative plate. 4 按照权利要求2或3所述铅酸蓄电池的制备方法,其特征在于分散剂是十二烷基苯磺酸钠、聚乙烯醇或羧甲基纤维素纳。4 according to the preparation method of the described lead-acid battery of claim 2 or 3, it is characterized in that the dispersant is sodium dodecylbenzenesulfonate, polyvinyl alcohol or sodium carboxymethyl cellulose. 5 按照权利要求4所述铅酸蓄电池的制备方法,其特征在于经预处理后的纳米碳质材料再在高温2000~3000℃下石墨化处理,然后再与分散剂混合。5. The preparation method of lead-acid battery according to claim 4, characterized in that the pretreated nano carbonaceous material is graphitized at a high temperature of 2000-3000°C, and then mixed with a dispersant. 6 按照权利要求5所述铅酸蓄电池的制备方法,其特征在于石墨化处理的温度为2200~2600℃。6. According to the preparation method of the lead-acid battery according to claim 5, it is characterized in that the temperature of the graphitization treatment is 2200-2600°C.
CNB021446806A 2002-12-04 2002-12-04 Lead-acid storage battery having added nano carbonaceous material and method for making same Expired - Fee Related CN1230929C (en)

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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
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
CN100367558C (en) * 2005-12-22 2008-02-06 上海交通大学 A method for prolonging the service life of sealed lead-acid batteries
ES2548549T3 (en) * 2011-06-23 2015-10-19 Molecular Rebar Design, Llc Lead and acid battery formulations containing discrete carbon nanotubes
TWI583043B (en) 2014-03-31 2017-05-11 長興材料工業股份有限公司 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
CN107732250B (en) * 2017-08-30 2020-07-21 淄博火炬能源有限责任公司 Rechargeable battery and method for manufacturing the same
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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