CN104157860B - sodium-selenium cell and preparation method thereof - Google Patents
sodium-selenium cell and preparation method thereof Download PDFInfo
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- CN104157860B CN104157860B CN201310175228.XA CN201310175228A CN104157860B CN 104157860 B CN104157860 B CN 104157860B CN 201310175228 A CN201310175228 A CN 201310175228A CN 104157860 B CN104157860 B CN 104157860B
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 invention discloses a kind of sodium selenium cell and preparation method thereof.This sodium selenium cell comprises metallic sodium negative pole, selenium porous carrier complex positive pole and organic electrolyte.Described selenium porous carrier complex positive pole is mixed post-heating by selenium by a certain percentage with porous carrier and makes, and selenium is dispersed in the micropore canals of porous carrier with short chain shape molecular forms.Described porous carrier includes carbon porous carrier, non-carbon porous carrier and combinations thereof thing.The sodium selenium cell that the present invention provides can keep high circulation volume, excellent stable circulation and good high magnification (high current density discharge and recharge) performance in the large temperature range including room temperature, the preparation method of its key component selenium porous carrier complex positive pole is simple, raw material is easy to get, suitable for mass production, possess the highest practicality.
Description
Technical field
The invention belongs to field of electrochemical power source, be specifically related to a kind of sodium-selenium cell and preparation method thereof, and described
Receive-selenium cell application in high volume energy density type energy storage device.
Background technology
Sodium selenium cell refers to that using elemental selenium or selenium-containing compound is positive pole, and metallic sodium is negative pole, by between selenium and sodium
Bielectron electrochemical reaction realize between chemical energy and electric energy one class novel metal sodium rechargeable battery of mutually conversion.Sodium selenium electricity
Chi Zhong, the selenium as positive pole and the sodium as negative pole are respectively provided with the highest theoretical capacity, and it is the highest that this makes sodium selenium cell have
Theoretical energy density, adapts to the development trend of mobile device strict to volumetric constraint at present.
Selenium and sulfur are same major element, therefore sodium selenium cell with at present in intelligent grid and distributed power station extensively
The sodium-sulphur battery used has a lot of similarity.Although the theoretical capacity of selenium is less than sulfur, but it has higher voltage and bigger
Density so that sodium selenium cell has the theoretical energy density suitable with sodium-sulphur battery.In tradition sodium-sulphur battery, owing to sulfur exists
With the electrochemical reaction hypoactivity of sodium under room temperature, and in charge and discharge process, it is easily formed that a series of to be soluble in electrolyte many
Sulfide, thus there is the problem (usually less than 20 circle) that sulfur positive pole utilization rate is low, Capacity fading is fast, have a strong impact on room
The performance of the lower sodium-sulphur battery of temperature and actual application.Therefore, the operating temperature of tradition sodium-sulphur battery existsAbove, this
Make sodium-sulphur battery need additional heating equipment to maintain temperature in the course of the work, be greatly increased its operating cost；Meanwhile,
Owing to when sodium-sulphur battery works, sodium and sulfur are all in liquid, once earthenware generation breakage i.e. forms short circuit, now, high temperature
Liquid Sodium will directly contact with sulfur and violent exothermic reaction occurs, and has a strong impact on the safety that sodium-sulphur battery runs.With sulfur
Comparing, the electrical conductivity of selenium exceeds 20 orders of magnitude so that it is at room temperature the electrochemical reaction activity with sodium is far above sulfur, thus
The utilization rate of positive active material is greatly improved, and is suitable for the needs of high current charge-discharge；Meanwhile, selenium is at charge and discharge process
Many selenides of middle formation dissolubility in the electrolytic solution is less so that it is just having higher cyclical stability than sulfur.Although
Selenium relatively costly, but by selenium and sodium assembled battery with low cost, can effectively reduce the manufacturing cost of battery.Therefore, sodium selenium
Battery can meet the demand that room temperature uses, so that it compares tradition sodium-sulphur battery has more preferable safety and energy warp
Ji property, may replace tradition sodium-sulphur battery and meets the application demand including the storage of large-scale fixed energy and electric automobile.
Although this novel sodium selenium cell has the many merits such as energy density is high, safety is high, but at present to sodium selenium
The research of battery is the rarest, is still not clear selenium as electrode material activity material reaction mechanism in charge and discharge process.
Not long ago, Amine et al. (J.Am.Chem.Soc.2012,134,4505-4508) is to the charge and discharge in sodium selenium cell of the selenium positive pole
Electricity response mechanism has carried out the research work of exploration, and the sodium selenium cell of its exploitation uses metallic sodium to be negative pole, selenium and carbon nanometer
The mixture of pipe is positive pole.Owing to the size of granules of selenium is effectively combined more greatly and not with conductive substrates, make the electrification of selenium
Learn activity to can not get effectively playing, so that the sodium selenium cell circulation volume arrived is low.Simultaneously as conductive substrates is to selenium
Dispersion and restriction effect more weak, the selenium of a part can form many selenides in cyclic process and is dissolved in electrolyte, causes sodium
The capacity of selenium cell carries out occurring irreversible decay with circulation, thus have impact on the service life of battery.
CN101794844A disclose a kind of copper fluoride-selenium nanometer composite cathode material for lithium ion battery and
Preparation method, wherein forms nano composite material by the way of laser splash by copper fluoride and elemental selenium, and multiple by this nanometer
Condensation material as the negative material of lithium-ion film cell, but, the electro-chemical activity of this negative material is low, and capacity is managed not
Think, it is impossible to be used in sodium selenium cell.
CN102623678A discloses a kind of Li Se battery and the preparation method of electrode material of lithium battery, it is disclosed that
The method using thermal evaporation at Grown selenium micron ball and is being loaded with the Grown selenium nanowires of Au catalyst or is receiving
Rice band, as lithium battery material, but owing to needing use Precious Metals-Gold in this invention, and selenium steam is in the atmosphere of circulation
Reaction, can cause again the significant wastage of selenium, and additionally selenium is deposited on substrate surface, and effect instability easily comes off, it is most important that,
In the invention selenium as positive electrode to lithium brownout (about 0.25V), therefore cannot with sodium positive pole pairing assemble sodium selenium
Battery (sodium lithium voltage is about 0.3V).
CN102938475A discloses a kind of sodium-sulphur battery and preparation method thereof, and wherein disclosed sodium-sulphur battery comprises gold
Belong to sodium negative pole, sulfur porous carrier complex positive pole and organic electrolyte.In described sulfur porous carrier complex, sulfur is with short chain shape
Sulfur molecule form is stored in the duct of porous carrier.Although micropore canals can be to a certain degree to the confinement effect of sulfur molecule
The dissolution of upper alleviation sulfur, but due to the electrochemical properties of sulfur itself, sulfur positive pole is the most inevitably given birth in charge and discharge process
Become to be soluble in many sulphions of electrolyte, thus compromise the long-term cyclicity of sodium-sulphur battery.Meanwhile, this sodium-sulphur battery is defeated
Go out voltage relatively low (average 1.4V), reduce its energy density the most to a certain extent.
It is not difficult to find out from above analysis, selects the conductive substrates with Suitable porous structure, selenium is carried out with conductive substrates
Effectively compound, selenium is limited in the duct of substrate with the form of molecule simultaneously, thus preparation have high volume energy density and
The lithium selenium cell electrode material of cyclical stability, exploitation has the lithium selenium cell of high power capacity and stable circulation performance, for whole
The development in individual energy storage field also has great importance.
Summary of the invention
It is an object of the invention to provide a kind of sodium-sulfur battery and preparation method thereof.
The invention provides a kind of selenium porous carrier complex for sodium selenium cell, described complex is by selenium and micropore
Carrier is prepared, and described selenium is dispersed in the micropore canals of described porous carrier with the form of chain molecule；Described selenium
Weight/mass percentage composition in described porous carrier is 20 93%.In the composite that the method obtains, selenium can be with stable
Nano shape is present in the duct of carrier, and the present inventor it has surprisingly been found that, use the method to obtain
Composite as the positive electrode of sodium-ion battery, can keep high circulation volume, excellent steady in large temperature range
Determine cyclicity and good high magnification (high current density discharge and recharge) performance, its key component selenium porous carrier complex
The preparation method of positive pole is simple, and raw material is easy to get, suitable for mass production, possesses the highest practicality.
On the basis of above-mentioned discovery, the present invention further provides a kind of sodium selenium cell, including the metal as negative pole
Sodium, as the selenium porous carrier composite electrode of positive pole and organic electrolyte, described selenium porous carrier composite electrode is by selenium
Porous carrier composite positive pole and conductive additive, binding agent and solvent prepare, it is characterised in that described selenium micropore
Carrier complexes positive electrode is prepared by selenium and porous carrier, and described selenium is dispersed in described with the form of chain molecule
In the micropore canals of porous carrier；Described selenium weight/mass percentage composition in described porous carrier is 20 93%.
Preferably, porous carrier finger-hole footpath described herein carrier material between 0.2 2nm.
In above-mentioned complex, one or more in carbon porous carrier and non-carbon porous carrier of described porous carrier；
Described carbon porous carrier is to possess certain electric conductivity and the carbon carrier of microcellular structure or a combination thereof thing；
Described non-carbon porous carrier is chosen in particular from micropore conducting polymer (miroporous conductive
Polymer), micropore metal (miroporous metal), micropore metal oxide (microporous metal oxide),
Micropore semiconductive ceramic (miroporous semi conductive ceramic), micropore metal organic backbone (metal
Organic framework) coordination polymer, one in non-carbon molecular sieve (non carbon molecular sieve) or
Multiple；
Wherein, during described micropore conducting polymer is selected from polyaniline, polyacetylene, polyhenylene, polypyrrole and polythiophene
Plant or multiple；
Described micropore metal one in micropore gold, micropore platinum, micropore aluminum, micropore ruthenium, microporous nickel and micropore titanium or
Multiple；
Described micropore metal oxide one in micropore ferroso-ferric oxide, Microporous titania and microporous alumina ruthenium
Or it is multiple；
One or more in micro-pore silicon carbide and microporous alumina zinc of described micropore semiconductive ceramic；
Described micropore metal organic backbone coordination polymer is equal selected from MIL 100 (Cr), MIL 101 (Cr) and MOF 5(
For trade name, MIL is the abbreviation of Materiaux Institut Lavoisier company, and MOF is metal organic
The abbreviation of framework) at least one；
Described non-carbon micro porous molecular sieve one in 3A molecular sieve, 5A molecular sieve, 10X molecular sieve and 13X molecular sieve
Or it is multiple.
The specific surface area of described porous carrier is 200 4500m2g‐1, specifically can be preferably 300m2g-1、920m2g‐1、
4000m2g‐1, pore volume is 0.1 3.0cm3g‐1, specifically can be preferably 0.5cm3g‐1、0.2cm3g‐1、2cm3g‐1, average pore size is
0.2 2nm, specifically can be preferably 0.6nm, 1.2nm, 1.6nm, or more preferably 0.6 1.2nm.
The method preparing described selenium porous carrier complex that the present invention provides, comprises the steps: selenium micro-with described
It is warming up under inert gas shielding after the carrier mixing of holeInsulation, then stop heating and be cooled to room temperature, obtain institute
State selenium porous carrier complex.
In said method, described selenium is 0.25 13:1 with the mass ratio of described porous carrier, and preferably 0.5 10:1 is more excellent
Select 0.5 4:1；
Described noble gas is the gas that nitrogen, argon, helium etc. do not react with selenium or porous carrier；
In described heating step, heating rate ismin‐1；
In described incubation step, the time is 2 20 hours.
The present invention also provides for the selenium porous carrier complex positive pole and preparation method thereof for sodium selenium cell, and this selenium is micro-
Hole carrier complexes positive pole contains described selenium porous carrier complex, binding agent and conductive additive.Prepare described selenium micropore
Carrier complexes positive pole specifically includes following steps: by described selenium porous carrier complex and conductive additive, binding agent and molten
Agent mixes by a certain percentage, through slurrying, smear, be dried etc. technological process i.e. obtain selenium porous carrier complex positive pole.
In said method, described conductive additive is one or more in carbon black, Super P, Ketjen black；
In said method, described binding agent and solvent are that Kynoar (PVDF) (is with N methyl pyrrolidone (NMP)
Solvent) or polyacrylic acid (PAA), sodium carboxymethyl cellulose (CMC), sodium alginate (SA), gelatin (all with water as solvent) in
One or more.
The sodium selenium cell that the present invention provides, including metallic sodium negative pole, selenium porous carrier complex positive pole and organic electrolysis
Liquid.
In above-mentioned battery, described organic electrolyte is carbonic ester electrolyte or ether electrolyte, and concentration is 0.1 2M, is preferably
0.5‐1.5M；
In described carbonic ester electrolyte, solvent is selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl methyl carbonate
(EMC) at least one, in ethylene carbonate (EC) and Allyl carbonate (PC), solute is selected from sodium hexafluoro phosphate (NaPF6), high
Sodium chlorate (NaClO4), one or more in sodium iodide (NaI) and two (trimethyl fluoride sulfonyl) imines sodium (NaTFSI)；
In described ether electrolyte, solvent is selected from 1,3 dioxolanes (DOL), glycol dimethyl ether (DME) and triethylene glycol
At least one in dimethyl ether (TEGDME), solute is selected from sodium hexafluoro phosphate (NaPF6), sodium perchlorate (NaClO4), sodium iodide
(NaI) one or more in and two (trimethyl fluoride sulfonyl) imines sodium (NaTFSI).
The operating temperature of described sodium selenium cell isIt is speciallyOr
It addition, the application that the sodium selenium cell of the invention described above offer is in preparation high-energy density type energy storage device, also belong to
In protection scope of the present invention.
Accompanying drawing explanation
Fig. 1 is the Raman spectrogram of the selenium microporous carbon complex of embodiment 1.
Fig. 2 is that the sodium selenium cell of embodiment 1 cyclic voltammogram in carbonic ester electrolyte (sweeps speed: 0.05mVs‐1).
Fig. 3 is the sodium selenium cell of embodiment 1 charging and discharging curve under 0.1C multiplying power in carbonic ester electrolyte.
Fig. 4 is the sodium selenium cell of embodiment 1 cycle performance under 0.1C multiplying power in carbonic ester electrolyte.
Fig. 5 is the sodium selenium cell of embodiment 1 charging and discharging curve under 1C multiplying power in carbonic ester electrolyte.
Fig. 6 is the sodium selenium cell of embodiment 1 cycle performance under 1C multiplying power in carbonic ester electrolyte.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
Experimental technique described in following embodiment, if no special instructions, is conventional method；Described reagent and material, all
Commercially obtain.
Embodiment 1
(1) selenium porous carrier complex is prepared
The porous carrier used in experiment is microporous carbon (purchased from Kuraray company), and specific surface area is 920m2g‐1, hole
Hold for 0.50cm3g‐1, average pore size is 0.6nm, and in prepared selenium microporous carbon complex, the mass fraction of selenium is 50%.
The preparation method of selenium microporous carbon complex is as follows:
(1) ratio of selenium with microporous carbon 1:1 in mass ratio is weighed and uniformly mixed；
(2) by the mixture of selenium and microporous carbon under nitrogen atmosphere is protected withmin‐1Heating rate be heated toAnd maintain heating 12h, make selenium fully dispersed in microporous carbon；
(3) stop heating and drop back to room temperature, obtaining selenium microporous carbon complex.
Fig. 1 is the Raman spectrogram of described selenium microporous carbon composite, can be at 260cm‐1Place observes chain selenium molecule
Characteristic peak, illustrate selenium presented in chain molecule in micropore canals.
(2) selenium porous carrier complex positive pole is prepared
By the selenium microporous carbon complex of above-mentioned preparation and carbon black, binding agent polyvinylidene fluoride 8:0.5:1.5 in mass ratio
Mixing, and add solvent N methyl pyrrolidone, through slurrying, smear, be dried etc. technological process i.e. obtain selenium microporous carbon complex
Positive pole.
(3) sodium selenium cell is assembled
With sodium negative pole, the selenium microporous carbon complex positive pole of above-mentioned preparation is assembled sodium selenium cell, and electrolyte selects carbonic ester
Electrolyte (1M NaClO4EC/DMC(mass ratio be 1:1) solution).
(4) sodium selenium cell test
Use discharge and recharge instrument that above-mentioned sodium selenium cell carries out constant current charge-discharge test, use electrochemical workstation to above-mentioned
Sodium selenium cell is circulated volt-ampere test, and test voltage interval is 0.8 2.7V.Test temperature isBattery capacity and filling
Discharge current is all with the Mass Calculation of selenium.Fig. 2 be described sodium selenium cell cyclic voltammogram in carbonic ester electrolyte (sweep speed:
0.05mV s‐1), described sodium selenium cell occurs a reduction peak (～1.1V) in first circle cathodic process, in first circle anodic process
Corresponding there is an oxidation peak (～1.6V).From the beginning of the second circle, described sodium selenium cell occurs two reduction in cathodic process
Peak (～1.5V and～1.3V), the most only occurs an oxidation peak (～1.6V) in anodic process, and in circulation subsequently,
The most there is not significant change in reduction peak and the position of oxidation peak, intensity and peak shape, illustrates that battery reaches after the second circle circulation
Electrochemically stable state.
Fig. 3 is that described sodium selenium cell 0.1C multiplying power in carbonic ester electrolyte (is equivalent to 68mA g‐1Discharge and recharge under) is bent
Line.Starting to engender slope from 2.0V in first circle discharge process, main capacity contribution in below 1.5V, first circle discharge capacity is
940mA h g‐1, coulombic efficiency is 70%, second circle start, the capacity contribution in discharge process be concentrated mainly on 1.75V and
On slope between 1.25V, and after the second circle, discharge capacity is always stable at 650mA h g‐1Left and right, coulombic efficiency begins
Being maintained at more than 98% eventually, cycle performance is good.Fig. 4 is described sodium selenium cell following under 0.1C multiplying power in carbonic ester electrolyte
Ring performance.Described sodium selenium cell is through 20 circle circulations, and capacity still has 645mA h g‐1.Fig. 5 is that described sodium selenium cell is at carbonic acid
In ester electrolyte, 1C multiplying power (is equivalent to 680mA g‐1Charging and discharging curve under).Described sodium selenium cell discharge and recharge under 1C multiplying power
There is not significant change in curve shape and battery polarization relatively 0.1C, and discharge capacity is stable at 550mA after the 3rd circle circulation
h g‐1Left and right, has good cyclical stability.Fig. 6 is described sodium selenium cell following under 1C multiplying power in carbonic ester electrolyte
Ring performance.After 100 circle circulations, the discharge capacity of described sodium selenium cell remains at 440mA h g‐1Left and right, demonstrates excellent
Different capability retention and good high rate capability.
Comparative example 1.1
Other condition is same as in Example 1, the difference is that only that the carbon carrier used when preparing selenium carbon complex is
The macropore carbon of average pore size about 200nm, the first circle charging capacity recorded after being assembled into sodium selenium cell is 410mA h g‐1, the
Two circles start, and capacity is gradually stable at 60mA h g‐1Left and right.
Embodiment 2
Other condition is same as in Example 1, the difference is that only when preparing selenium porous carrier complex positive pole, bonding
Sodium carboxymethyl cellulose is selected in agent, and solvent selects water, and the first circle recorded under 0.1C multiplying power after being assembled into sodium selenium cell discharges
Capacity is 920mA h g‐1, first circle charging capacity is 630mA h g‐1, the second circle starts, and capacity is gradually stable at 620mA h g‐1Left and right.Through 20 circle circulations, the capacity of described sodium selenium cell is still maintained at 600mA h g‐1Left and right.Described sodium selenium cell
Capacity under 1C electric current density remains at 520mA hg‐1, under 1C multiplying power, circulate the discharge capacity after 100 circles remain at
390mA h g‐1Left and right.
Embodiment 3
(1) selenium porous carrier complex positive pole is prepared
The porous carrier used in experiment is micropore ferroso-ferric oxide (purchased from Sigma Aldrich), specific surface area
For 300m2g‐1, pore volume is 0.2cm3g‐1, average pore size is 1.6nm, selenium in prepared selenium micropore ferroferric oxide compound
Mass fraction be 35%.
The preparation method of selenium micropore ferroferric oxide compound is as follows:
(1) ratio of selenium with micropore ferroso-ferric oxide 35:65 in mass ratio is weighed and uniformly mixed；
(2) by the mixture of selenium and micropore ferroso-ferric oxide with min‐1Heating rate be heated toAnd tie up
Hold heating 6h, make selenium fully dispersed in micropore ferroso-ferric oxide；
(3) stop heating and drop back to room temperature, obtaining selenium micropore ferroferric oxide compound.
(2) selenium porous carrier complex positive pole is prepared
By the selenium micropore ferroferric oxide compound of above-mentioned preparation and Super P, binding agent gelatin and water in mass ratio 7:
2:1 mixing mixing, through slurrying, smear, be dried etc. technological process i.e. obtain selenium micropore ferroferric oxide compound positive pole.
(3) sodium selenium cell is assembled
With sodium negative pole, the selenium micropore ferroferric oxide compound positive pole of above-mentioned preparation is assembled sodium selenium cell, and electrolyte selects
Select ether electrolyte (0.5M LiClO4DOL/DME(mass ratio be 1:1) solution).
(4) sodium selenium cell test
Using discharge and recharge instrument that above-mentioned sodium selenium cell is carried out constant current charge-discharge test, test voltage interval is 0.8 2.5V.
Test temperature isBattery capacity and charging and discharging currents are all with the Mass Calculation of selenium.Described sodium selenium cell is at above-mentioned voltage
In interval, the first circle discharge capacity under 0.1C multiplying power is 1050mA h g‐1, first circle charging capacity is 670mA h g‐1, the second circle
Starting, capacity is gradually stable at 650mA h g‐1Left and right.Described sodium selenium cell circulates through 100 circles under 0.1C multiplying power, capacity
Remain at 610mA h g‐1Left and right.
Embodiment 4
(1) selenium porous carrier complex positive pole is prepared
The porous carrier used in experiment be micropore metal organic backbone coordination polymer (MIL 100 (Cr), for chromium and
The coordination polymer that trimesic acid is formed, purchased from Materiaux Institut Lavoisier company), specific surface area is
4000m2g‐1, pore volume is 2cm3g‐1, average pore size is 1.2nm, in prepared selenium micropore metal organic framework material complex
The mass fraction of selenium is 85%.
The preparation method of selenium micropore metal organic framework material complex is as follows:
(1) ratio of selenium with micropore metal organic framework material 85:15 in mass ratio is weighed and uniformly mixed；
(2) by the mixture of selenium and micropore metal organic framework material with min‐1Heating rate be heated toAnd maintain heating 18h, make selenium fully dispersed in micropore metal organic framework material；
(3) stop heating and drop back to room temperature, obtaining selenium micropore metal organic framework material complex.
(2) selenium porous carrier complex positive pole is prepared
By the selenium micropore metal organic framework material complex of above-mentioned preparation and Ketjen black, binding agent carboxymethyl cellulose
Sodium and water 6:2:2 in mass ratio mixing, through slurrying, smear, be dried etc. technological process i.e. obtain selenium micropore metal organic backbone material
Material complex positive pole.
(3) sodium selenium cell is assembled
The selenium micropore metal organic framework material complex positive pole of above-mentioned preparation is assembled sodium selenium cell, electricity with sodium negative pole
Solve liquid and select carbonic ester electrolyte (1M LiClO4PC/EMC(mass ratio be 2:1) solution).
(4) sodium selenium cell test
Using discharge and recharge instrument that above-mentioned sodium selenium cell is carried out constant current charge-discharge test, test voltage interval is 0.8 2.7V.
Test temperature isBattery capacity and charging and discharging currents are all with the Mass Calculation of selenium.Described sodium selenium cell is at above-mentioned voltage
In interval, the first circle discharge capacity under 0.1C multiplying power is 760mA h g‐1, first circle charging capacity is 450mA h g‐1, the second circle is opened
Beginning, capacity is gradually stable at 420mA h g‐1Left and right.Described sodium selenium cell is through 50 circle circulations under 0.1C multiplying power, and capacity is still
It is maintained at 390mA h g‐1Left and right.
Comparative example 4.1
Other condition is the same as in Example 4, the difference is that only the coordination polymerization used when preparing selenium carbon complex
Thing carrier be average pore size be the mesoporous supports of 10nm.Obtained sodium selenium cell is after same method of testing test, first
Circle discharge capacity is 500mA h g‐1, the second circle starts, and capacity is gradually stable at 310mAh g‐1Left and right.
In sum, the sodium selenium cell of the present invention can possess high following in the large temperature range including room temperature
Ring capacity, excellent room temperature cycles stability and good high rate performance, its key component selenium porous carrier complex is just
The preparation method of pole is simple, and raw material is easy to get, suitable for mass production.Although selenium is relatively costly, but by selenium with low cost
Sodium assembled battery, can effectively reduce the manufacturing cost of battery.Meanwhile, compared with the lithium selenium cell reported at present, described room temperature
Sodium selenium cell there is the more preferable economy of energy (cost of sodium is substantially less than lithium), be more suitable for heavy industrialization, and can have
Effect alleviates the current secondary battery industry demand to lithium resource.Thus the sodium selenium cell of the present invention is expected to as a kind of novel
High-energy-density energy storage device, and have a good application prospect.
Claims (1)
1. a sodium selenium cell, it is prepared by following step:
(1) selenium porous carrier complex is prepared
The porous carrier used is the micropore ferroso-ferric oxide purchased from Sigma Aldrich, and specific surface area is 300m2g‐1,
Pore volume is 0.2cm3g‐1, average pore size is 1.6nm, the mass fraction of selenium in prepared selenium micropore ferroferric oxide compound
It is 35%；
The preparation method of selenium micropore ferroferric oxide compound is as follows:
(1) ratio of selenium with micropore ferroso-ferric oxide 35:65 in mass ratio is weighed and uniformly mixed；
(2) by the mixture of selenium and micropore ferroso-ferric oxide with 2 DEG C of min‐1Heating rate be heated to 230 DEG C and maintain heating
6h, makes selenium fully dispersed in micropore ferroso-ferric oxide；
(3) stop heating and drop back to room temperature, obtaining selenium micropore ferroferric oxide compound；
(2) selenium porous carrier complex positive pole is prepared
By the selenium micropore ferroferric oxide compound of above-mentioned preparation and Super P, binding agent gelatin and water 7:2:1 in mass ratio
Mixing, through slurrying, smear, is dried to obtain selenium micropore ferroferric oxide compound positive pole；
(3) sodium selenium cell is assembled
With sodium negative pole, the selenium micropore ferroferric oxide compound positive pole of above-mentioned preparation is assembled sodium selenium cell, and electrolyte selects
DOL/DME mass ratio is 1:1, LiClO4Concentration is the electrolyte of 0.5M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310175228.XA CN104157860B (en) | 2013-05-13 | 2013-05-13 | sodium-selenium cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310175228.XA CN104157860B (en) | 2013-05-13 | 2013-05-13 | sodium-selenium cell and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104157860A CN104157860A (en) | 2014-11-19 |
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| US11588149B2 (en) | 2015-09-22 | 2023-02-21 | Ii-Vi Delaware, Inc. | Immobilized selenium in a porous carbon with the presence of oxygen, a method of making, and uses of immobilized selenium in a rechargeable battery |
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| CN105633361B (en) * | 2015-12-25 | 2018-05-11 | 清华大学深圳研究生院 | Sodium ion battery electrode material, its preparation method and battery |
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| US11870059B2 (en) * | 2017-02-16 | 2024-01-09 | Consejo Superior De Investigaciones Cientificas (Csic) | Immobilized selenium in a porous carbon with the presence of oxygen, a method of making, and uses of immobilized selenium in a rechargeable battery |
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| CN111342016A (en) * | 2020-03-09 | 2020-06-26 | 肇庆市华师大光电产业研究院 | Sodium-selenium battery positive electrode material and preparation method thereof |
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