CN108199032A - The preparation of the hollow bismuth simple substance of carbon-coated nano and its alkaline battery application - Google Patents
The preparation of the hollow bismuth simple substance of carbon-coated nano and its alkaline battery application Download PDFInfo
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- CN108199032A CN108199032A CN201810055854.8A CN201810055854A CN108199032A CN 108199032 A CN108199032 A CN 108199032A CN 201810055854 A CN201810055854 A CN 201810055854A CN 108199032 A CN108199032 A CN 108199032A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
Abstract
The present invention relates to the preparation of the hollow bismuth simple substance of carbon-coated nano and its alkaline battery application studies, belong to alkaline battery technical field.Though nano metal bismuth has good electric conductivity and electrochemical properties, structural stability is poor in electrolyte environment.To improve its stability and cycle efficieny, we have proposed the effective ways being limited in nano-hollow bismuth in carbon microreactor, this method is specially：First, hollow fluorine bismuth ammonium is synthesized by room temperature liquid phase method（NH4Bi3F10）Presoma；Then, the carbon coating of presoma is realized using dopamine molecule polymerization at room temperature；Finally, low-temperature carbonization processing is carried out to products therefrom, obtains the hollow bismuth simple substance of carbon-coated nano.When applied to alkaline battery, which can show superior high rate performance and cyclic durability.Involved preparation process is very simple, easily accomplishes scale production and product structure property is stablized, have practical application foreground and commercial value.
Description
Technical field
The invention belongs to alkaline battery technical fields, and in particular to a kind of preparation method of alkaline battery negative electrode material and should
With.
Background technology
As the problems such as fossil energy exhaustion and environmental degradation, is on the rise, green energy resource（Including wind energy, tide energy and too
Sun can wait）Development and utilization become particularly important.Though these energy can be transformed into electric energy and have sustainability, it is utilized
Often it is limited by the extraneous factors such as time, place, weather.For convenience of daily life demand, development battery system is converted to collect
The electric energy come is current most effective strategy.In recent years, lithium battery is in chargeable energy storage field in occupation of leading position.However,
The problem of current lithium battery but faces many sternnesses further includes battery explosion, old and useless battery other than the mining deposits such as lithium are deficient
Pollution and safe retrieving etc., the root of problem is all related to the severe toxicity of organic electrolyte, inflammability.Safety is developed as a result,
Heavy-duty battery is the important trend developed now.
Compared to lithium battery, the electrolyte of alkaline battery is common aqueous solution, cheap and low toxicity.At present, there are many classes
It can charge and discharge alkaline battery system（Including nickel-hydrogen, Ni-Fe, nickel-bismuth battery etc.）It is suggested.It is emphasized that novel bismuthino
Alkaline battery is just by the common concern of global scientific research circle, for example, the flat seminars of the Liu Jin of Wuhan University of Technology are in the recent period just in titanium
It directly grown bismuth oxide nano thin-film on metal electrode, and be used in alkaline battery energy storage field.But unfortunately, almost
The bismuth system negative material of all exploitations all poor for electric conductivity oxide or hydroxide, this will directly affect the quick of battery
Charge-discharge characteristic.It compares, bismuth metal simple substance has superior electric conductivity and electrochemical reaction activity, and theoretical specific capacity is remote
Higher than other bismuth system oxide/hydroxide.However, bismuth metal simple substance is easily corroded and aoxidizes in electrolyte environment, change
Structural stability is poor, this has become the fatal problem that the material is further applied and developed.
To improve its stability, the bismuth system alkaline battery of quick charge and discharge point function is realized, we have proposed by nano-hollow
Bismuth is limited to the efficient synthesis in carbon microreactor, and this method is specially：First, nanometer is synthesized by room temperature liquid phase method
Hollow fluorine bismuth ammonium（NH4Bi3F10）Presoma；Then, the cladding of presoma is realized using dopamine molecule polymerization at room temperature；
Finally, low-temperature carbonization processing is carried out to products therefrom, you can the hollow bismuth simple substance of carbon-coated nano is made.On the one hand, hollow gold
Belong to bismuth nanometer configuration and provide larger specific surface area, electrode is made fully to be contacted with electrolysis liquid energy, accelerates the electrification of system
Learn reaction rate；On the other hand, hollow nano metal bismuth forms preferable synergistic effect with carbon shell.Internal bismuth metal tool
Standby excellent electric conductivity and electro-chemical activity, and external carbon-coating then enhances the steady chemical structure of bismuth kernel, effectively
Inhibit fragmentation and the agglomeration of active matter.It is emphasized that the preparation method and condition are all very simple, rule are easily realized
Modelling produces and product structure property is stablized, and has practical application foreground and commercial value.
Invention content
In consideration of it, it is an object of the invention to：（1）A kind of preparation method of carbon-clad metal nano-hollow bismuth is provided；（2）
There is provided a kind of cobalt/nickel-bismuth high power density can the full battery of charge and discharge alkalinity.
In order to achieve the above objectives, the present invention provides following technical solution：
1. the preparation of the hollow bismuth simple substance of carbon-coated nano and its alkaline battery application, include the following steps：
（1）Materials synthesis：Using bismuth salt and villiaumite as raw material, them is made to be reacted in reaction dissolvent, using room temperature liquid phase method and
Low-temperature carbonization handles to obtain the hollow bismuth composite negative pole material of carbon-coated nano；
（2）Prepare electrode slice：Negative material, conductive agent and bonding agent are added in solvent, stirring at ambient temperature is made black
The thick slurry of color, and be applied on collector electrode, the electricity of the hollow bismuth simple substance of carbon-coated nano is obtained after drying process
Pole；
（3）Electrode activation and performance detection：It is right using cyclic voltammetry scan method（2）In the hollow bismuth of carbon-coated nano obtained
The electrode of simple substance is activated；To be activated to finish, the constant current charge-discharge and cycle performance that different multiplying is carried out to electrode slice detect；
（4）Full battery assembling and test：By carbon coating CoNi3O4Nano-array film positive plate is used as anode, by step（3）
The carbon-clad metal nano-hollow bismuth simple substance electrode of activation is used as cathode, and the sodium hydroxide solution of 6 mol/L is used as electrolyte, fine
The plain filter paper of dimension is used as diaphragm material, successively stacks anode, diaphragm, cathode, injects its thermoplastic package after electrolyte saturating
In bright polyethylene film, that is, complete the assembling of alkaline cobalt/full battery of nickel-bismuth；Then full battery is tested for the property.
Further, the step（1）In bismuth salt for five nitric hydrate bismuths, villiaumite is ammonium fluoride, and reaction dissolvent is second two
Alcohol.
Further, the step（2）Described in conductive agent be carbon black；The step（2）In bonding agent be polyvinylidene fluoride
Alkene（PVdF）；The step（2）In solvent be N-Methyl pyrrolidone；The step（2）In collector electrode be foam
Nickel.
Further, the step（2）The mass ratio of middle negative material, conductive agent and bonding agent is 8：1：1.
Further, the step（2）Middle drying process is 120o10 hours are stood under C baking conditions.
Further, the step（3）In electrode activation comprise the steps of：By step（2）In carbon coating obtained receive
The hollow bismuth simple substance electrode of rice is immersed in 6 mol/L sodium hydroxide solutions, and using Ag/AgCl as reference electrode, platinum electrode is
To electrode, 100-200 circle cyclic voltammetry scan processes are carried out to electrode with the rate of 50 mV/s on electrochemical workstation.
Further, the step（4）In carbon coating CoNi3O4The preparation method of nano-array film positive plate is：It will
0.7 g Ni(NO3)2·6H2O、0.4 g Co(NO3)2·6H2O、0.2 g NH4F and 0.75 g CO (NH2)2Ultrasonic disperse in
In the distilled water of 50 mL；Then, above-mentioned mixed liquor is transferred in the reaction kettle liner of 100 mL, a stainless steel substrates（Ruler
It is very little：40×25×0.5 mm）It immerses in the solution, 120 after reaction kettle is sealedoIt is reacted 4 hours under C constant temperatures；It treats anti-
After kettle is answered to cool down, take out stainless steel substrates and with distilled water flushing three times, and be immersed in containing 0.1 g dopamines（DA）Molecule
Solution in；After room temperature leaching puts 6 hours, take out stainless steel substrates and with its surface of distilled water flushing, sample is then placed in argon gas
600 in the quartz tube furnace of atmosphereoC is heated 1 hour.
Further, the step（4）In full battery testing in negative plate and positive plate mass ratio be 7：10.
2. the beneficial effects of the present invention are：The invention discloses a kind of effective, low cost novel carbon-clad metals
The preparation method of nano-hollow bismuth and its application on alkaline battery.When applied to alkaline battery, which can show
Go out superior high rate performance and cyclic durability.Involved preparation process is very simple, easily accomplishes scale production and product
Structural property is stablized, and has practical application foreground and commercial value.
Description of the drawings
In order to make the purpose of the present invention, technical solution and advantageous effect clearer, the present invention provides drawings described below and carries out
Explanation：
Fig. 1 is the scanning electron microscope diagram of negative material used in embodiment 1（a）And X-ray diffraction（XRD）Spectrogram（b）；
Fig. 2 is the discharge curve of the different current densities of negative material used in embodiment 2；
Fig. 3 is the specific volume spirogram under negative material difference current density used in embodiment 2（a）With cycle life figure（b）；
Fig. 4 is the discharge curve of 2 full battery difference current density of embodiment；
Fig. 5 is the specific volume spirogram under 2 full battery difference current density of embodiment（a）With cycle life figure（b）.
Specific embodiment
Below in conjunction with attached drawing, the preferred embodiment of the present invention is described in detail.
The synthesis of 1 carbon-clad metal nano-hollow bismuth negative material of embodiment
（1）Fluorine bismuth ammonium（NH4Bi3F10）The synthesis of presoma：Take 0.2 g Bi (NO3)3·6H2The NH of O and 0.6 g4F is put respectively
Vortex dissolving is carried out in the ethylene glycol centrifuge tube containing 25 mL.Above two solution is uniformly mixed, room temperature 12 hours
Afterwards, after filter washing, 60oTo sample drying 8 hours to get NH under the conditions of C4Bi3F10Persursor material.
（2）The synthesis of carbon-clad metal nano-hollow bismuth negative material：Take 0.4 g NH4Bi3F10It adds in more containing 0.1 g
Stirring at normal temperature 6 hours in the solution of bar amine molecule, centrifuges and is simultaneously repeatedly rinsed with absolute ethyl alcohol, then 60oBy sample under the conditions of C
Product are dried 8 hours and obtain grey NH4Bi3F10@PDA nanometer powders.Then, 400 under ar gas environmentoC low-temperature carbonizations 30 minutes
Obtain carbon-clad metal nano-hollow bismuth material.The visible Fig. 1 of sample result.
Fig. 1（a）For products therefrom microscopic appearance, surface sample presentation hollow Nano is spherical, and average-size is about 70
nm.Fig. 1（b）X-ray diffraction for product（XRD）Material phase analysis is as a result, as seen from the figure, obtained sample diffraction peak and standard
Card peak is consistent, illustrates that by sample made from such method be bismuth metal material.
Embodiment 2 is made using carbon-clad metal nano-hollow bismuth as the full battery of the alkalinity of cathode and test method
（1）Cathode pole piece makes：By negative material and conductive agent and binding agent in mass ratio 8:1:After 1 ratio mixing, add
Enter appropriate N-Methyl pyrrolidone solvent and stir 12 hours, obtain dark thick shape slurry.Slurry is uniformly smeared with scraper
On foamed nickel current collector electrode, 120oC is dried in vacuo 12 hours to get cathode pole piece.
（2）Electrode slice activates and test：By step（2）In electrode slice obtained be used as working electrode, Ag/AgCl and platinum filament
Respectively reference electrode and to electrode, 6 mol/L sodium hydroxide solutions are electrolyte, and speed is swept in electrochemistry work with 50 mV/s
By step on standing（2）In electrode cycle obtained scanning 100-200 circles.After to be activated, electrode slice is carried out not synchronized
The cyclic voltammetry and constant current charge-discharge test of rate.Embodiment result is shown in Fig. 2 and Fig. 3.
（3）Full battery assembling and test：By carbon coating CoNi3O4Nano-array film positive plate is used as working battery, carbon packet
The hollow bismuth of metal nano is covered as cathode, and the sodium hydroxide solution of 6 mol/L is used as electrolyte, and cellulosic filter paper is used as diaphragm
Material.Anode, diaphragm, cathode are stacked successively, injected after electrolyte by its thermoplastic package in cellothene, i.e., it is complete
Into the assembling of full battery.After full battery after cyclic voltammetric activates a few, different rates are carried out on electrochemical workstation
Cyclic voltammetry and constant current charge-discharge test.Embodiment result is shown in Fig. 4 and Fig. 5.
Fig. 2 is the constant-current discharge under different current densities of obtained carbon-clad metal nano-hollow bismuth negative material
Curve.As can be seen that when discharge current density changes to 32 A/g from 1 A/g, the charge and discharge platform of battery does not occur big
Change, show the excellent electrochemical kinetics characteristic of the material system.
Fig. 3（a）The specific volume spirogram for being electrode under different current densities.Under 1 A/g discharge current densities, electrode specific volume
Amount is up to 110 mAh/g；When i.e. convenient current density reaches 32 A/g, capacity can still maintain 83 mAh/g, it was demonstrated that carbon
Coat the superior high rate performance of the hollow bismuth of metal nano.Fig. 3（b）It is the cycle life figure of electrode, it is close in the electric current of 0.5 A/g
After the lower charge and discharge cycles 10000 of degree are enclosed, specific capacity is substantially almost without larger attenuation, and capacity retention ratio is up to 96%, fully
Confirm that the cycle performance of carbon-clad metal nano-hollow bismuth is very excellent.
Fig. 4 is obtained cobalt/constant-current discharge curve of the full battery of nickel-bismuth under different current densities.It can be seen that
Under 0.5 A/g discharge current densities, the main discharge platform of the full battery is 0.9 V；I.e. convenient current density increases more than 30 times
（Reach 16 A/g）When, the main discharge platform of the full battery can still maintain 0.8 V or so.
Fig. 5（a）For the battery specific capacity calculated according to Fig. 4, under the current density of 0.5,1,2,4,8,16 A/g, the material
The charging and discharging capacity of material is respectively 80,72,63,57,48,36.5 mAh/g, has reflected cobalt/full battery of nickel-bismuth herein
High rate performance.Fig. 5（b）It is the full battery in 0.5 A/g/Cycle life figure under current density, through 2000 charge and discharge cycles
After test, the capacity retention ratio of full battery fully reflects its larger practical application potentiality still up to 88%.
Claims (8)
1. the preparation of the hollow bismuth simple substance of carbon-coated nano and its alkaline battery application, which is characterized in that include the following steps：（1）
Materials synthesis：Using bismuth salt and villiaumite as raw material, them is made to be reacted in reaction dissolvent, using room temperature liquid phase method and low-temperature carbonization
Processing obtains the hollow bismuth composite negative pole material of carbon-coated nano；（2）Prepare electrode slice：By negative material, conductive agent and bonding agent
It adds in solvent, stirs dark thick shape slurry is made, and be applied on collector electrode at ambient temperature, at drying
The hollow bismuth simple substance electrode slice of carbon-coated nano is obtained after reason；（3）Electrode activation and performance detection：Utilize cyclic voltammetry scan side
Method is right（2）In the hollow bismuth simple substance electrode of carbon-coated nano obtained activated；It is to be activated to finish, electrode slice is carried out different
Constant current charge-discharge and the cycle performance detection of multiplying power；（4）Full battery assembling and test：By carbon coating CoNi3O4Nano-array film
Positive plate is used as anode, by step（3）The carbon-clad metal nano-hollow bismuth simple substance electrode activated is used as cathode, 6 mol/L
Sodium hydroxide solution be used as electrolyte, cellulosic filter paper is used as diaphragm material；Anode, diaphragm, cathode are stacked successively, note
Enter its thermoplastic package after electrolyte in cellothene, that is, complete the assembling of alkaline cobalt/full battery of nickel-bismuth, and
Performance detection is carried out to full battery afterwards.
2. the preparation of the hollow bismuth simple substance of carbon-coated nano according to claim 1 and its alkaline battery application, feature exist
In the step（1）In bismuth salt for five nitric hydrate bismuths, villiaumite is ammonium fluoride, and reaction dissolvent is ethylene glycol.
3. the preparation of the hollow bismuth simple substance of carbon-coated nano according to claim 1 and its alkaline battery application, feature exist
In the step（2）Described in conductive agent be carbon black；The step（2）In bonding agent be Kynoar（PVdF）；It is described
Step（2）In solvent be N-Methyl pyrrolidone；The step（2）In collector electrode be nickel foam.
4. the preparation of the hollow bismuth simple substance of carbon-coated nano according to claim 1 and its alkaline battery application, feature exist
In the step（2）The mass ratio of middle negative material, conductive agent and bonding agent is 8：1：1.
5. the preparation of the hollow bismuth simple substance of carbon-coated nano according to claim 1 and its alkaline battery application, feature exist
In the step（2）Middle drying process is 120o10 hours are stood under C baking conditions.
6. the preparation of the hollow bismuth simple substance of carbon-coated nano according to claim 1 and its alkaline battery application, feature exist
In the step（3）In electrode slice activation comprise the steps of：By step（2）In the hollow bismuth list of carbon-coated nano obtained
The electrode slice of matter is immersed in 6 mol/L sodium hydroxide solutions, and using Ag/AgCl as reference electrode, platinum electrode is to electricity
Pole carries out electrode slice with the rate of 50 mV/s on electrochemical workstation 100-200 circle cyclic voltammetry scan processes.
7. the preparation of the hollow bismuth simple substance of carbon-coated nano according to claim 1 and its alkaline battery application, feature exist
In the step（4）In carbon coating CoNi3O4The preparation method of nano-array film positive plate is：By 0.7 g Ni
(NO3)2·6H2O、0.4 g Co(NO3)2·6H2O、0.2 g NH4F and 0.75 g CO (NH2)2Ultrasonic disperse is in the steaming of 50 mL
In distilled water；Then, above-mentioned mixed liquor is transferred in the reaction kettle liner of 100 mL, a stainless steel substrates（Size：40×25×
0.5 mm）It immerses in the solution, 120 after reaction kettle is sealedoIt is reacted 4 hours under C constant temperatures；After reaction kettle cooling,
Take out stainless steel substrates and with distilled water flushing three times, and be immersed in containing 0.1 g dopamines（DA）In the solution of molecule；Room
After temperature leaching puts 6 hours, take out stainless steel substrates and with its surface of distilled water flushing, sample is then placed in the quartz ampoule of argon atmosphere
600 in formula stoveoC is heated 1 hour.
8. the preparation of the hollow bismuth simple substance of carbon-coated nano according to claim 1 and its alkaline battery application, feature exist
In the step（4）In full battery testing in negative plate and positive plate mass ratio be 7：10.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111769272A (en) * | 2020-07-28 | 2020-10-13 | 广西师范大学 | Bi @ C hollow nanosphere composite material and preparation method and application thereof |
| CN113161530A (en) * | 2021-03-10 | 2021-07-23 | 广州大学 | Bismuth-based nano material and preparation method and application thereof |
| CN113823785A (en) * | 2021-09-18 | 2021-12-21 | 山东省科学院新材料研究所 | Hollow mesoporous carbon shell coated metal nanosphere and super-assembly preparation method and application thereof |
| CN114023953A (en) * | 2021-11-03 | 2022-02-08 | 惠州亿纬锂能股份有限公司 | Modified lithium iron manganese phosphate cathode material and preparation method and application thereof |
| CN114171807A (en) * | 2021-12-13 | 2022-03-11 | 西南大学 | Low temperature resistant river system nickel-iron battery |
| CN114335484A (en) * | 2022-01-05 | 2022-04-12 | 徐州博磊达新能源科技有限公司 | Negative electrode composite material for alkali metal ion battery, preparation method of negative electrode composite material and alkali metal ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111769272A (en) * | 2020-07-28 | 2020-10-13 | 广西师范大学 | Bi @ C hollow nanosphere composite material and preparation method and application thereof |
| CN113161530A (en) * | 2021-03-10 | 2021-07-23 | 广州大学 | Bismuth-based nano material and preparation method and application thereof |
| CN113823785A (en) * | 2021-09-18 | 2021-12-21 | 山东省科学院新材料研究所 | Hollow mesoporous carbon shell coated metal nanosphere and super-assembly preparation method and application thereof |
| CN114023953A (en) * | 2021-11-03 | 2022-02-08 | 惠州亿纬锂能股份有限公司 | Modified lithium iron manganese phosphate cathode material and preparation method and application thereof |
| CN114171807A (en) * | 2021-12-13 | 2022-03-11 | 西南大学 | Low temperature resistant river system nickel-iron battery |
| CN114335484A (en) * | 2022-01-05 | 2022-04-12 | 徐州博磊达新能源科技有限公司 | Negative electrode composite material for alkali metal ion battery, preparation method of negative electrode composite material and alkali metal ion battery |
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| CN108199032B (en) | 2020-02-07 |
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