CN101635353A - Method for preparing compound electrode active material of nickel hydroxide/carbon nano tube - Google Patents
Method for preparing compound electrode active material of nickel hydroxide/carbon nano tube Download PDFInfo
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- CN101635353A CN101635353A CN200910114320A CN200910114320A CN101635353A CN 101635353 A CN101635353 A CN 101635353A CN 200910114320 A CN200910114320 A CN 200910114320A CN 200910114320 A CN200910114320 A CN 200910114320A CN 101635353 A CN101635353 A CN 101635353A
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- 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
Abstract
The invention discloses a method for preparing a compound electrode active material of a nickel hydroxide/carbon nano tube. Under strong stirring , nickel hydroxide particles generated by rapid reaction of soluble nickel salt and strong base are attached on the surface of the carbon nano tube so as to obtain the compound electrode active material of the nickel hydroxide/carbon nano tube. The method is simple and convenient to operate and the condition is easy to control; the prepared compound electrode active material of the nickel hydroxide/carbon nano tube has excellent heavy-current charging and discharging performance and favorable circulation performance, and is suitable for being used as the alkaline battery anode active material.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the compound electrode active material of nickel hydroxide/carbon nano tube of alkaline battery.
Background technology
But the alkaline hydrogen nickel-based battery is described as first-selected electric vehicle power accumulator because of its energy density height, the fast charging and discharging that has extended cycle life, memory-less effect, excellent comprehensive characteristic such as pollution-free.In the Ni-H cell, the performance of positive active material is the key that cell integrated combination property improves, and especially as the electric motor car power accumulator, the high rate during charging-discharging of nickel electrode also needs further to improve.
Nickel hydroxide is a kind of material with semiconductor property, and the resistance between its granule interior and the particle is very big, and causing nickel hydroxide is not very desirable as the performance of active material assembled battery.At present, the researcher is mainly by carrying out the internal metal ion substitute doping to its positive electrode active materials nickel hydroxide, means such as its surface coats are further improved the performance of Ni-H cell, and it mainly acts on is to strengthen its conductivity, improve oxygen evolution potential, improve high temperature efficiency for charge-discharge etc.Yet, under the high current charge-discharge condition, electrochemical reaction mainly concentrates on the top layer of nickel hydroxide particle carries out, because of the resistance of nickel hydroxide very big, its granule interior depths active material under this kind condition, be difficult to be fully utilized, thereby the specific capacity that discharges and recharges reduces.So, improve the combination property of hydrogen nickel power accumulator, must solve its problems referred to above that in the middle of battery applications, exist.
Summary of the invention
The purpose of this invention is to provide a kind of compound electrode active material of nickel hydroxide/carbon nano tube preparation method that can improve the Ni-H cell high rate during charging-discharging, the direct spread loads of nickel hydroxide particulate of utilizing the on-the-spot generation in liquid phase of chemical coprecipitation handle is in carbon nano tube surface, make the two become a kind of composite material, the conductive network that carbon nano-tube forms in composite material not only can improve the inner and intergranular conductivity of nickel hydroxide particle, and can also suppress the expansion of nickel electrode effectively.This compound electrode active material of nickel hydroxide/carbon nano tube has excellent high rate during charging-discharging, high power capacity and good cyclical stability.
Concrete steps of the present invention are:
(1) be that the multi-walled carbon nano-tubes of 10-100nm joins in the mixed acid solution that volume ratio is 3: 1 the concentrated sulfuric acid and red fuming nitric acid (RFNA) sonicated 1-3 hour with caliber; Adding distil water dilution back suction filtration is washed with distilled water to neutrality, is dried to constant weight in 70 ℃;
(2) be the ratio of 1-5% in the mass percent of carbon nano-tube in target product, take by weighing through step (1) mixed acid processed carbon nanotubes join in the soluble nickel salting liquid mixed solution A, the organic solvent that adds volume ratio simultaneously and be above-mentioned mixed solution A 1-5% is made dispersant, ultrasonic concussion 30-60 minute forms the mixed liquid B that even carbon nanotube is disperseed;
(3) mol ratio that adds in step (2) gained mixed liquid B with nickel salt is 2: 1 strong base solutions, and 60 ℃ of stirring reactions 2 hours are deposited in 60 ℃ of ageings 10 hours in mother liquor with gained;
The precipitation suction filtration that (4) will obtain is washed with distilled water to neutrality, is dried to constant weight in 60 ℃, is the finished product compound electrode active material of nickel hydroxide/carbon nano tube.
Described soluble nickel salt is a kind of in nickelous sulfate, nickel nitrate and the nickel chloride, and the concentration of nickelous sulfate, nickel nitrate and nickel chloride is respectively 0.5-2mol/L, 0.1-2mol/L and 0.1-1mol/L;
Described dispersant is a kind of in methyl alcohol, ethanol, propyl alcohol, acetone and the butanone;
Described highly basic is a kind of in NaOH, potassium hydroxide and the lithium hydroxide, and the concentration of NaOH, potassium hydroxide and lithium hydroxide is respectively 0.5-4mol/L, 0.5-5mol/L and 0.5-3mol/L.
Described carbon nano-tube is that caliber is the multi-walled carbon nano-tubes of 10-100nm.
The present invention utilizes chemical coprecipitation to make the on-the-spot direct spread loads of nickel hydroxide particulate that generates in liquid phase the two become a kind of composite material in carbon nano tube surface.Synthesis technique of the present invention is simple, method of operation is easy, condition is easy to control, has improved the high rate during charging-discharging and the cycle performance of sample.
Description of drawings
Fig. 1 is the XRD figure of the nickel hydroxide/carbon nano tube composite material of the embodiment of the invention 1.
Fig. 2 is the SEM figure of the nickel hydroxide/carbon nano tube composite material of the embodiment of the invention 1.
Fig. 3 is the discharge curve of the nickel hydroxide/carbon nano tube composite material of the embodiment of the invention 1.
Fig. 4 be the embodiment of the invention 1 the nickel hydroxide/carbon nano tube composite material the cycle performance curve.
Embodiment
Embodiment 1:
The mass percentage content of carbon nano-tube is the preparation of 1% nickel hydroxide/carbon nano tube composite material.
The present embodiment carbon nano-tube is that caliber is the multi-walled carbon nano-tubes of 10-30nm.
Carbon nano-tube is joined in the mixed acid solution that volume ratio is 3: 1 the concentrated sulfuric acid and red fuming nitric acid (RFNA) sonicated 3 hours.Adding distil water dilution back suction filtration is washed with distilled water to neutrality, is dried to constant weight in 70 ℃.By the mass percent of carbon nano-tube in target product is 1% to take by weighing through the nitration mixture processed carbon nanotubes and join in the nickel nitrate solution of 0.5mol/L, the ethanol that adds volume ratio simultaneously and be above-mentioned solution 2% is made dispersant, ultrasonic concussion 30 minutes forms the mixed liquor that even carbon nanotube is disperseed.The mol ratio that adds with nickel salt is the sodium hydroxide solution of 2: 1 1mol/L, and 60 ℃ of stirring reactions 2 hours are deposited in 60 ℃ of ageings 10 hours in mother liquor with gained.Precipitation suction filtration with obtaining is washed with distilled water to neutrality, is dried to constant weight in 60 ℃, is the finished product compound electrode active material of nickel hydroxide/carbon nano tube.Products therefrom is indicated as the β nickel hydroxide through X-ray diffraction analysis.Products obtained therefrom is made simulated battery under the 1C multiplying power, discharges and recharges, its first discharge capacity be 278mAhg
-1, the 50th time discharge capacity is 273mAhg
-1
Embodiment 2: the mass percentage content of carbon nano-tube is the preparation of 3% nickel hydroxide/carbon nano tube composite material.
The present embodiment carbon nano-tube is that caliber is the multi-walled carbon nano-tubes of 40-60nm.Carbon nano-tube is joined in the mixed acid solution that volume ratio is 3: 1 the concentrated sulfuric acid and red fuming nitric acid (RFNA) sonicated 2 hours.Adding distil water dilution back suction filtration is washed with distilled water to neutrality, is dried to constant weight in 70 ℃.By the mass percent of carbon nano-tube in target product is 3% to take by weighing and an amount of join in the nickel sulfate solution of 0.5mol/L through the nitration mixture processed carbon nanotubes, the propyl alcohol that adds volume ratio simultaneously and be above-mentioned solution 3% is made dispersant, ultrasonic concussion 30 minutes forms the mixed liquor that even carbon nanotube is disperseed.The mol ratio that adds with nickel salt is the potassium hydroxide solution of 2: 1 1mol/L, and 60 ℃ of stirring reactions 2 hours are deposited in 60 ℃ of ageings 10 hours in mother liquor with gained.Precipitation suction filtration with obtaining is washed with distilled water to neutrality, is dried to constant weight in 60 ℃, is the finished product compound electrode active material of nickel hydroxide/carbon nano tube.Products obtained therefrom is made simulated battery under the 1C multiplying power, discharges and recharges, its first discharge capacity be 275mAhg
-1, the 50th time discharge capacity is 270mAhg
-1
Embodiment 3: the mass percentage content of carbon nano-tube is the preparation of 5% nickel hydroxide/carbon nano tube composite material.
The present embodiment carbon nano-tube is that caliber is the multi-walled carbon nano-tubes of 60-100nm.Carbon nano-tube is joined in the mixed acid solution that volume ratio is 3: 1 the concentrated sulfuric acid and red fuming nitric acid (RFNA) sonicated 1 hour.Adding distil water dilution back suction filtration is washed with distilled water to neutrality, is dried to constant weight in 70 ℃.By the mass percent of carbon nano-tube in target product is 5% to take by weighing and an amount of join in the nickel chloride solution of 0.5mol/L through the nitration mixture processed carbon nanotubes, the acetone that adds volume ratio simultaneously and be above-mentioned solution 4% is made dispersant, ultrasonic concussion 30 minutes forms the mixed liquor that even carbon nanotube is disperseed.The mol ratio that adds with nickel salt is the lithium hydroxide solution of 2: 1 1mol/L, and 60 ℃ of stirring reactions 2 hours are deposited in 60 ℃ of ageings 10 hours in mother liquor with gained.Precipitation suction filtration with obtaining is washed with distilled water to neutrality, is dried to constant weight in 60 ℃, is the finished product compound electrode active material of nickel hydroxide/carbon nano tube.Products obtained therefrom is made simulated battery under the 1C multiplying power, discharges and recharges, its first discharge capacity be 274mAhg
-1, the 50th time discharge capacity is 270mAhg
-1
Claims (2)
1. the preparation method of a compound electrode active material of nickel hydroxide/carbon nano tube is characterized in that may further comprise the steps:
(1) be that the multi-walled carbon nano-tubes of 10-100nm joins in the mixed acid solution that volume ratio is 3: 1 the concentrated sulfuric acid and red fuming nitric acid (RFNA) sonicated 1-3 hour with caliber; Adding distil water dilution back suction filtration is washed with distilled water to neutrality, is dried to constant weight in 70 ℃;
(2) be the ratio of 1-5% in the mass percent of carbon nano-tube in target product, take by weighing through step (1) mixed acid processed carbon nanotubes join in the soluble nickel salting liquid mixed solution A, the organic solvent that adds volume ratio simultaneously and be above-mentioned mixed solution A 1-5% is made dispersant, ultrasonic concussion 30-60 minute forms the mixed liquid B that even carbon nanotube is disperseed;
(3) mol ratio that adds in step (2) gained mixed liquid B with nickel salt is 2: 1 strong base solutions, and 60 ℃ of stirring reactions 2 hours are deposited in 60 ℃ of ageings 10 hours in mother liquor with gained;
The precipitation suction filtration that (4) will obtain is washed with distilled water to neutrality, is dried to constant weight in 60 ℃, is the finished product compound electrode active material of nickel hydroxide/carbon nano tube;
Described soluble nickel salt is a kind of in nickelous sulfate, nickel nitrate and the nickel chloride, and the concentration of nickelous sulfate, nickel nitrate and nickel chloride is respectively 0.5-2mol/L, O.1-2mol/L and 0.1-1mol/L;
Described dispersant is a kind of in methyl alcohol, ethanol, propyl alcohol, acetone and the butanone;
Described highly basic is a kind of in NaOH, potassium hydroxide and the lithium hydroxide, and the concentration of NaOH, potassium hydroxide and lithium hydroxide is respectively 0.5-4mol/L, 0.5-5mol/L and 0.5-3mol/L.
2. preparation method according to claim 1 is characterized in that described carbon nano-tube is that caliber is the multi-walled carbon nano-tubes of 10-100nm.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101908389A (en) * | 2010-07-30 | 2010-12-08 | 广西师范大学 | Preparation method for activated carbon/carbon nano tube mixed electrode material, and product thereof and application |
| CN103943372A (en) * | 2014-05-08 | 2014-07-23 | 扬州大学 | Nickel hydroxide/multi-walled carbon nanotube composite material and preparation method thereof |
| CN104916457A (en) * | 2015-05-25 | 2015-09-16 | 淮北师范大学 | Electrochemical capacitor and electro-adsorption desalination electrode material |
| CN105449194A (en) * | 2015-12-21 | 2016-03-30 | 江苏理工学院 | Cathode material for nickel-zinc battery and nickel-zinc battery employing cathode material |
| CN109777075A (en) * | 2019-01-25 | 2019-05-21 | 华研(佛山)纳米材料有限公司 | A kind of polycarbonate electromagnetic shielding material of carbon nanotubes and preparation method thereof |
| WO2020224573A1 (en) * | 2019-05-08 | 2020-11-12 | 广州理文科技有限公司 | Manufacturing methods for porous nano-nickel network structure based on crown ether supermolecule bound silver ions, supercapacitor electrode and supercapacitor |
| CN112044442A (en) * | 2020-09-04 | 2020-12-08 | 郑州大学 | Preparation method and application of beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects |
| CN113488639A (en) * | 2021-07-01 | 2021-10-08 | 肇庆市华师大光电产业研究院 | Preparation method of high-sulfur-content lithium-sulfur battery positive electrode material |
| CN114105224A (en) * | 2021-11-23 | 2022-03-01 | 黑龙江工程学院 | Preparation method and application of nickel hydroxide/carbon nano tube composite nanosheet |
-
2009
- 2009-08-19 CN CN200910114320A patent/CN101635353A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101908389A (en) * | 2010-07-30 | 2010-12-08 | 广西师范大学 | Preparation method for activated carbon/carbon nano tube mixed electrode material, and product thereof and application |
| CN103943372A (en) * | 2014-05-08 | 2014-07-23 | 扬州大学 | Nickel hydroxide/multi-walled carbon nanotube composite material and preparation method thereof |
| CN104916457A (en) * | 2015-05-25 | 2015-09-16 | 淮北师范大学 | Electrochemical capacitor and electro-adsorption desalination electrode material |
| CN104916457B (en) * | 2015-05-25 | 2018-08-10 | 淮北师范大学 | A kind of electrochemical capacitor and Electro Sorb desalination electrode material |
| CN105449194A (en) * | 2015-12-21 | 2016-03-30 | 江苏理工学院 | Cathode material for nickel-zinc battery and nickel-zinc battery employing cathode material |
| CN105449194B (en) * | 2015-12-21 | 2019-03-19 | 江苏理工学院 | Zinc-nickel cell positive electrode and preparation method thereof and the zinc-nickel cell for using the positive electrode |
| CN109777075A (en) * | 2019-01-25 | 2019-05-21 | 华研(佛山)纳米材料有限公司 | A kind of polycarbonate electromagnetic shielding material of carbon nanotubes and preparation method thereof |
| WO2020224573A1 (en) * | 2019-05-08 | 2020-11-12 | 广州理文科技有限公司 | Manufacturing methods for porous nano-nickel network structure based on crown ether supermolecule bound silver ions, supercapacitor electrode and supercapacitor |
| CN112044442A (en) * | 2020-09-04 | 2020-12-08 | 郑州大学 | Preparation method and application of beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects |
| CN112044442B (en) * | 2020-09-04 | 2022-12-13 | 郑州大学 | Preparation method and application of beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects |
| CN113488639A (en) * | 2021-07-01 | 2021-10-08 | 肇庆市华师大光电产业研究院 | Preparation method of high-sulfur-content lithium-sulfur battery positive electrode material |
| CN113488639B (en) * | 2021-07-01 | 2022-08-26 | 肇庆市华师大光电产业研究院 | Preparation method of high-sulfur-content lithium-sulfur battery positive electrode material |
| CN114105224A (en) * | 2021-11-23 | 2022-03-01 | 黑龙江工程学院 | Preparation method and application of nickel hydroxide/carbon nano tube composite nanosheet |
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Open date: 20100127 |