CN104157860A - Sodium-selenium cell and preparation method thereof - Google Patents

Sodium-selenium cell and preparation method thereof Download PDF

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CN104157860A
CN104157860A CN201310175228.XA CN201310175228A CN104157860A CN 104157860 A CN104157860 A CN 104157860A CN 201310175228 A CN201310175228 A CN 201310175228A CN 104157860 A CN104157860 A CN 104157860A
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selenium
sodium
micropore
porous carrier
electrolyte
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CN104157860B (en
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郭玉国
辛森
殷雅侠
万立骏
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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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
    • 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
    • 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
    • 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
    • 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 sodium-selenium cell and a preparation method thereof. The sodium-selenium cell comprises a metal sodium negative electrode, a selenium-microporous carrier complex positive electrode and an organic electrolyte. The selenium-microporous carrier complex positive electrode is prepared from selenium and a microporous carrier by mixing in a certain proportion and then heating, the selenium is evenly dispersed in microporous pores of the microporous carrier in short chain molecule form, and the microporous carrier comprises a carbon microporous carrier, a non carbon microporous carrier and a composition thereof. The sodium-selenium cell can maintain a high cycle capacity, excellent and stable cyclicity and good high ratio (large current high density charge and discharge) performance in a large temperature range including room temperature, the main component selenium-microporous carrier complex positive electrode has the advantages of simple preparation method, easy obtained raw materials, suitability for mass production, and very high practicability.

Description

Sodium-selenium cell and preparation method thereof
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 in the application of receive-selenium cell in high volume energy density type energy storage device.
Background technology
Na ?selenium cell refer to and adopt simple substance selenium or selenium-containing compound for anodal, sodium metal is negative pole, by the bielectron electrochemical reaction between selenium and sodium, realizes between chemical energy and electric energy a class novel metal sodium rechargeable battery of conversion mutually.Na ?in selenium cell, as anodal selenium with as the sodium of negative pole, all there is very high theoretical capacity, this make Na ?selenium cell there is very high theoretical energy density, adapt to the development trend to the strict mobile device of volume restrictions at present.
Selenium and sulphur are same major element, thus sodium ?selenium cell with at present in intelligent grid and distributed power station widely used sodium ?sulphur battery have a lot of similitudes.Although the theoretical capacity of selenium is lower than sulphur, it has higher voltage and larger density, make Na ?selenium cell have Yu Na ?the suitable theoretical energy density of sulphur battery.Tradition Na ?in sulphur battery, because sulphur is at room temperature active low with the electrochemical reaction of sodium, and in charge and discharge process, easily form a series of polysulfides that are soluble in electrolyte, thereby there is the problem (being usually less than 20 circles) that the anodal utilance of sulphur is low, Capacity fading is fast, have a strong impact on Na Xia room temperature ?performance performance and the practical application of sulphur battery.Therefore, traditional Na ?the working temperature of sulphur battery exist above, this make Na ?sulphur battery need in the course of the work additional heating equipment to carry out holding temperature, greatly increase its operating cost; Meanwhile, due to sodium ?sulphur when battery operated sodium and sulphur be all in liquid state, once earthenware generation breakage forms short circuit, now, the Liquid Sodium of high temperature will directly contact and violent exothermic reaction occurs with sulphur, has a strong impact on the fail safe of sodium ?sulphur battery operation.Compare with sulphur, the conductivity of selenium exceeds 20 orders of magnitude, make its at room temperature with the electrochemical reaction activity of sodium far above sulphur, thereby significantly improved the utilance of positive active material, and can adapt to the needs of high current charge-discharge; Meanwhile, the solubility of many selenides that selenium forms in charge and discharge process in electrolyte is less, makes it than sulphur, just have higher cyclical stability.Although the cost of selenium is higher, by selenium and sodium assembled battery with low cost, can effectively reduce the manufacturing cost of battery.Therefore Na ?selenium cell can meet the demand that room temperature is used, thereby make it compare traditional sodium ?sulphur battery, there is better fail safe and the economy of energy, can replace traditional sodium ?sulphur battery and meet the application demand that comprises large-scale fixed stored energy and electric automobile.
Although this novel sodium ?selenium cell has the many merits such as energy density is high, fail safe is high, at present very rare to the research of sodium ?selenium cell, to selenium, as electrode material activity material, the reaction mechanism in charge and discharge process is still not clear.Not long ago, the people such as Amine (J.Am.Chem.Soc.2012,134,4,505 4508) to the anodal Na of selenium ?the reaction mechanism that discharges and recharges in selenium cell carried out exploratory research work, its exploitation Na ?selenium cell to adopt sodium metal be negative pole, the mixture of selenium and carbon nano-tube is positive pole.Because the size of granules of selenium more greatly and is not carried out effectively compoundly with conductive substrates, make the electro-chemical activity of selenium can not get effective performance, thereby make the sodium ?selenium cell circulation volume that obtains low.Simultaneously, due to conductive substrates to the dispersion of selenium and restriction a little less than, the selenium of a part can form many selenides and be dissolved in electrolyte in cyclic process, cause Na ?the capacity of selenium cell with looping, there is irreversible decay, thereby affected the useful life of battery.
CN101794844A discloses a kind of copper fluoride-selenium nanometer composite cathode material for lithium ion battery and preparation method thereof, wherein by copper fluoride and simple substance selenium, the mode by laser splash forms nano composite material, and by this nano composite material the negative material as lithium-ion film cell, but, the electro-chemical activity of this negative material is low, capacity is not ideal enough, cannot be used to Na ?in selenium cell.
CN102623678A disclose a kind of Li ?the preparation method of Se battery and electrode material of lithium battery, wherein disclose adopt thermal evaporation method at Grown selenium micron ball be loaded with Grown selenium nanowires or the nanobelt of Au catalyst, as lithium battery material, but owing to needing to use Precious Metals-Gold in this invention, and selenium steam reacts in the atmosphere of circulation, can cause the significant wastage of selenium again, selenium is deposited on substrate surface in addition, act on and unstablely easily coming off, the most important thing is, this invention in selenium as positive electrode to lithium brownout (about 0.25V), therefore cannot assemble sodium ?selenium cell (sodium lithium voltage is about to 0.3V) with the anodal pairing of sodium.
CN102938475A disclose a kind of Na ?sulphur battery and preparation method thereof, wherein disclosed Na ?sulphur power brick containing metal sodium negative pole, Liu ?porous carrier compound positive pole and organic electrolyte.Described Liu ?in porous carrier compound, sulphur is stored in the duct of porous carrier with short chain shape sulfur molecule form.Although micropore canals can be alleviated the stripping of sulphur to a certain extent to the confinement effect of sulfur molecule, but the electrochemical properties due to sulphur itself, sulphur positive pole still inevitably can generate the many sulphions that are soluble in electrolyte in charge and discharge process, thus damage Na ?the long-term cyclicity of sulphur battery.Meanwhile, Gai Na ?the output voltage of sulphur battery lower (average 1.4V), also reduced to a certain extent its energy density.
From above analysis, be not difficult to find out, selection has the conductive substrates of suitable loose structure, selenium and conductive substrates are carried out effectively compound, by selenium, the form with molecule is limited in the duct of substrate simultaneously, thereby preparation have high volume energy density and cyclical stability Li ?selenium cell electrode material, exploitation have high power capacity and stable circulation performance Li ?selenium cell, for the development in whole energy storage field, also have great importance.
Summary of the invention
The object of this invention is to provide a kind of sodium-sulfur battery and preparation method thereof.
The invention provides a kind of for Na ?selenium cell Xi ?porous carrier compound, described compound is by the preparation of selenium and porous carrier and obtain, described selenium is dispersed in the micropore canals of described porous carrier with the form of chain molecule; The quality percentage composition of described selenium in described porous carrier be 20 ?93%.In the composite material that the method obtains, selenium can be present in stable nano shape in the duct of carrier, and the present inventor finds unexpectedly, the composite material that employing the method obtains is as the positive electrode of sodium-ion battery, can in compared with large-temperature range, keep high circulation volume, the stable circulation of excellence and good high magnification (high current density discharges and recharges) performance, its chief component Xi ?the preparation method of porous carrier compound positive pole simple, raw material is easy to get, suitable for mass production, possesses very high practicality.
On the basis of above-mentioned discovery, the present invention further provides a kind of Na ?selenium cell, comprise sodium metal as negative pole, as anodal Xi ?porous carrier composite electrode and organic electrolyte, described Xi ?porous carrier composite electrode You Xi ?porous carrier composite positive pole and conductive additive, binding agent and solvent prepare, it is characterized in that described Xi ?porous carrier compound positive electrode by the preparation of selenium and porous carrier and obtain, described selenium is dispersed in the micropore canals of described porous carrier with the form of chain molecule; The quality percentage composition of described selenium in described porous carrier be 20 ?93%.
Preferably, the porous carrier finger-hole footpath described in the application 0.2 ?carrier material between 2nm.
In above-mentioned compound, described porous carrier is selected from one or more in carbon porous carrier and non-carbon porous carrier;
Described carbon porous carrier is carbon carrier or its composition that possesses certain conductivity and microcellular structure;
Described non-carbon porous carrier is specifically selected from micropore conducting polymer (miroporous conductive polymer), micropore metal (miroporous metal), micropore metal oxide (microporous metal oxide), micropore semiconductive ceramic (miroporous semi ?conductive ceramic), Wei Kong Jin Shu ?organic backbone (metal ?organic framework) Coordination Polymers, one or more in non-carbon molecular sieve (non ?carbon molecular sieve),
Wherein, described micropore conducting polymer is selected from one or more in polyaniline, polyacetylene, polyhenylene, polypyrrole and polythiophene;
Described micropore metal is selected from one or more in micropore gold, micropore platinum, micropore aluminium, micropore ruthenium, microporous nickel and micropore titanium;
Described micropore metal oxide is selected from one or more in micropore tri-iron tetroxide, micropore titanium dioxide and micropore ruthenium-oxide;
Described micropore semiconductive ceramic is selected from one or more in micro-pore silicon carbide and micropore zinc oxide;
Described Wei Kong Jin Shu ?organic backbone Coordination Polymers be selected from MIL ?100 (Cr), MIL ?101 (Cr) and MOF ?5(be trade name, MIL is the abbreviation of Materiaux Institut Lavoisier company, MOF be metal ?the abbreviation of organic framework) at least one;
Described non-carbon micro porous molecular sieve is selected from one or more in 3A molecular sieve, 5A molecular sieve, 10X molecular sieve and 13X molecular sieve.
The specific area of described porous carrier be 200 ?4500m 2g ?1, specifically can be preferably 300m 2g -1, 920m 2g ?1, 4000m 2g ?1, pore volume be 0.1 ?3.0cm 3g ?1, specifically can be preferably 0.5cm 3g ?1, 0.2cm 3g ?1, 2cm 3g ?1, average pore size be 0.2 ?2nm, specifically can be preferably 0.6nm, 1.2nm, 1.6nm, or more preferably 0.6 ?1.2nm.
The described Xi of preparation provided by the invention ?the method of porous carrier compound, after comprising the steps: selenium and described porous carrier to mix, under inert gas shielding, be warming up to insulation, then stop heating being cooled to room temperature, obtain described Xi ?porous carrier compound.
In said method, the mass ratio of described selenium and described porous carrier be 0.25 ?13:1, preferably 0.5 ?10:1, more preferably 0.5 ?4:1;
Described inert gas is the gas that nitrogen, argon gas, helium etc. do not react with selenium or porous carrier;
In described heating step, heating rate is min ?1;
In described incubation step, the time be 2 ?20 hours.
The present invention be also provided for Na ?selenium cell Xi ?porous carrier compound positive pole and preparation method thereof, Gai Xi ?porous carrier compound positive pole contain described Xi ?porous carrier compound, binding agent and conductive additive.Prepare described Xi ?porous carrier compound positive pole specifically comprise the steps: by described Xi ?porous carrier compound mix by a certain percentage with conductive additive, binding agent and solvent, through slurrying, smear, the technological process such as dry obtain Xi ?porous carrier compound anodal.
In said method, described conductive additive be carbon black, Super ?one or more in P, Ketjen black;
In said method, described binding agent and solvent are one or more in Kynoar (PVDF) (take N ?methyl pyrrolidone (NMP) be solvent) or polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC), sodium alginate (SA), gelatin (all take water as solvent).
Na provided by the invention ?selenium cell, comprise sodium metal negative pole, Xi ?porous carrier compound positive pole and organic electrolyte.
In above-mentioned battery, described organic electrolyte is carbonic ester electrolyte or ether electrolyte, concentration be 0.1 ?2M, be preferably 0.5 ?1.5M;
In described carbonic ester electrolyte, solvent is selected from least one in dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), ethylene carbonate (EC) and propene carbonate (PC), and solute is selected from sodium hexafluoro phosphate (NaPF 6), sodium perchlorate (NaClO 4), one or more in sodium iodide (NaI) and two (trimethyl fluoride sulfonyl) imines sodium (NaTFSI);
In described ether electrolyte, solvent be selected from 1,3 ?at least one in dioxolanes (DOL), glycol dimethyl ether (DME) and TRIGLYME (TEGDME), solute is selected from sodium hexafluoro phosphate (NaPF 6), sodium perchlorate (NaClO 4), one or more in sodium iodide (NaI) and two (trimethyl fluoride sulfonyl) imines sodium (NaTFSI).
Described Na ?the working temperature of selenium cell be be specially or
In addition, the invention described above provide Na ?the application of selenium cell in preparing high-energy-density type energy storage device, also belong to protection scope of the present invention.
Accompanying drawing explanation
Fig. 1 is the Raman spectrogram of the selenium ?microporous carbon compound of embodiment 1.
Fig. 2 be embodiment 1 Na ?the cyclic voltammogram of selenium cell in carbonic ester electrolyte (sweep speed: 0.05mVs ?1).
Fig. 3 be embodiment 1 Na ?selenium cell charging and discharging curve under 0.1C multiplying power in carbonic ester electrolyte.
Fig. 4 be embodiment 1 Na ?selenium cell cycle performance under 0.1C multiplying power in carbonic ester electrolyte.
Fig. 5 be embodiment 1 Na ?selenium cell charging and discharging curve under 1C multiplying power in carbonic ester electrolyte.
Fig. 6 be embodiment 1 Na ?selenium cell cycle performance under 1C multiplying power in carbonic ester electrolyte.
Embodiment
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 can obtain from commercial channels.
Embodiment 1
(1) prepare Xi ?porous carrier compound
The porous carrier adopting in experiment is microporous carbon (purchased from Japanese Kuraray company), and specific area is 920m 2g ?1, pore volume is 0.50cm 3g ?1, average pore size is 0.6nm, prepared Xi ?in microporous carbon compound the mass fraction of selenium be 50%.
Xi ?the preparation method of microporous carbon compound as follows:
(1) by selenium and microporous carbon in mass ratio the ratio of 1:1 weigh and evenly mix;
(2) by the mixture of selenium and microporous carbon under nitrogen atmosphere protection with min ?1heating rate be heated to and maintain heating 12h, make selenium fully be distributed in microporous carbon;
(3) stop heating and falling back room temperature, obtain Xi ?microporous carbon compound.
Fig. 1 is the Raman spectrogram of described selenium ?microporous carbon composite material, can be at 260cm ?1place observes the characteristic peak of chain selenium molecule, illustrates that selenium is present in micropore canals with the form of chain molecule.
(2) prepare Xi ?porous carrier compound anodal
By above-mentioned preparation Xi ?microporous carbon compound and carbon black, binding agent polyvinylidene fluoride in mass ratio 8:0.5:1.5 mix, and add solvent N ?methyl pyrrolidone, through slurrying, smear, the technological process such as dry obtain Xi ?microporous carbon compound anodal.
(3) assembling Na ?selenium cell
By above-mentioned preparation Xi ?microporous carbon compound positive pole with sodium negative pole assembling Na ?selenium cell, electrolyte is selected carbonic ester electrolyte (1M NaClO 4eC/DMC(mass ratio be 1:1) solution).
(4) Na ?selenium cell test
Use discharge and recharge instrument to above-mentioned Na ?selenium cell carry out constant current charge-discharge test, use electrochemical workstation to above-mentioned Na ?selenium cell carry out cyclic voltammetry, test voltage interval be 0.8 ?2.7V.Probe temperature is battery capacity and charging and discharging currents are all with the Mass Calculation of selenium.Fig. 2 be described Na ?the cyclic voltammogram of selenium cell in carbonic ester electrolyte (sweep speed: 0.05mV s ?1), described Na ?selenium cell in first circle cathodic process, there is a reduction peak (～1.1V), the corresponding oxidation peak (～1.6V) that occurs in first circle anodic process.Since the second circle, described Na ?selenium cell in cathodic process, there are two reduction peak (～1.5V and～1.3V), in anodic process, still only there is an oxidation peak (～1.6V), and in circulation subsequently, all there is not significant change in the position of reduction peak and oxidation peak, intensity and peak shape, illustrates that battery has reached electrochemical stability state after the second circle circulation.
Fig. 3 be described Na ?selenium cell 0.1C multiplying power in carbonic ester electrolyte (be equivalent to 68mA g ?1) under charging and discharging curve.In first circle discharge process, from 2.0V, start to engender slope, main capacity contribution is below 1.5V, and first circle discharge capacity is 940mA h g ?1, coulomb efficiency is that 70%, the second circle starts, the capacity contribution in discharge process mainly concentrates on the slope between 1.75V and 1.25V, and after the second circle, discharge capacity is stabilized in 650mA h g always ?1left and right, coulomb efficiency remains at more than 98%, and cycle performance is good.Fig. 4 be described Na ?selenium cell cycle performance under 0.1C multiplying power in carbonic ester electrolyte.Described Na ?selenium cell through 20 circles, circulate, capacity still has 645mA h g ?1.Fig. 5 be described Na ?selenium cell 1C multiplying power in carbonic ester electrolyte (be equivalent to 680mA g ?1) under charging and discharging curve.Described Na ?selenium cell charging and discharging curve shape and battery polarization under 1C multiplying power compared with 0.1C, there is not significant change, and discharge capacity is stabilized in 550mA h g after the 3rd circle circulation ?1left and right, has good cyclical stability.Fig. 6 be described Na ?selenium cell cycle performance under 1C multiplying power in carbonic ester electrolyte.After 100 circles circulations, described Na ?the discharge capacity of selenium cell still remain on 440mA h g ?1left and right, demonstrates excellent capability retention and good high rate capability.
Comparative example 1.1
Other condition is identical with embodiment 1, difference be only preparation Xi ?the carbon carrier that adopts during carbon complex be the macropore carbon of the about 200nm of average pore size, through be assembled into Na ?the first circle charging capacity that records after selenium cell be 410mA h g ?1, the second circle starts, and capacity is stabilized in 60mA h g gradually ?1left and right.
Embodiment 2
Other condition is identical with embodiment 1, difference be only to prepare Xi ?porous carrier compound when anodal, binding agent is selected sodium carboxymethylcellulose, and solvent is selected water, through be assembled into Na ?the first circle discharge capacity that records under 0.1C multiplying power after selenium cell be 920mA h g ?1, first circle charging capacity is 630mA h g ?1, the second circle starts, and capacity is stabilized in 620mA h g gradually ?1left and right.Through 20 circles circulations, described Na ?the capacity of selenium cell still remain on 600mA h g ?1left and right.Described Na ?the capacity of selenium cell under 1C current density still remain on 520mA hg ?1, the discharge capacity circulating after 100 circles under 1C multiplying power still remains on 390mA h g ?1left and right.
Embodiment 3
(1) prepare Xi ?porous carrier compound anodal
The porous carrier adopting in experiment be micropore tri-iron tetroxide (purchased from Sigma ?Aldrich company), specific area is 300m 2g ?1, pore volume is 0.2cm 3g ?1, average pore size is 1.6nm, prepared Xi ?in micropore ferroferric oxide compound the mass fraction of selenium be 35%.
Xi ?the preparation method of micropore ferroferric oxide compound as follows:
(1) by selenium and micropore tri-iron tetroxide in mass ratio the ratio of 35:65 weigh and evenly mix;
(2) by the mixture of selenium and micropore tri-iron tetroxide with min ?1heating rate be heated to and maintain heating 6h, selenium is fully distributed in micropore tri-iron tetroxide;
(3) stop heating and falling back room temperature, obtain Xi ?micropore ferroferric oxide compound.
(2) prepare Xi ?porous carrier compound anodal
By above-mentioned preparation Xi ?micropore ferroferric oxide compound and Super ?P, binding agent gelatin and water in mass ratio 7:2:1 mix, through slurrying, smear, the technological process such as dry obtain Xi ?micropore ferroferric oxide compound anodal.
(3) assembling Na ?selenium cell
By above-mentioned preparation Xi ?micropore ferroferric oxide compound positive pole with sodium negative pole assembling Na ?selenium cell, electrolyte is selected ether electrolyte (0.5M LiClO 4dOL/DME(mass ratio be 1:1) solution).
(4) Na ?selenium cell test
Use discharge and recharge instrument to above-mentioned Na ?selenium cell carry out constant current charge-discharge test, test voltage interval be 0.8 ?2.5V.Probe temperature is battery capacity and charging and discharging currents are all with the Mass Calculation of selenium.Described Na ?selenium cell first circle discharge capacity under 0.1C multiplying power in above-mentioned voltage range be 1050mA h g ?1, first circle charging capacity is 670mA h g ?1, the second circle starts, and capacity is stabilized in 650mA h g gradually ?1left and right.Described Na ?selenium cell under 0.1C multiplying power through 100 circles circulations, capacity still remains on 610mA h g ?1left and right.
Embodiment 4
(1) prepare Xi ?porous carrier compound anodal
The porous carrier adopting in experiment be Wei Kong Jin Shu ?organic backbone Coordination Polymers (MIL ?100 (Cr), the Coordination Polymers forming for chromium and trimesic acid, purchased from Materiaux Institut Lavoisier company), specific area is 4000m 2g ?1, pore volume is 2cm 3g ?1, average pore size is 1.2nm, prepared Xi ?in micropore metal organic framework material compound the mass fraction of selenium be 85%.
Xi ?the preparation method of micropore metal organic framework material compound as follows:
(1) by selenium and micropore metal organic framework material in mass ratio the ratio of 85:15 weigh and evenly mix;
(2) by the mixture of selenium and micropore metal organic framework material with min ?1heating rate be heated to and maintain heating 18h, selenium is fully distributed in micropore metal organic framework material;
(3) stop heating and falling back room temperature, obtain Xi ?micropore metal organic framework material compound.
(2) prepare Xi ?porous carrier compound anodal
By above-mentioned preparation Xi ?micropore metal organic framework material compound and Ketjen black, binding agent sodium carboxymethylcellulose and water in mass ratio 6:2:2 mix, through slurrying, smear, the technological process such as dry obtain Xi ?micropore metal organic framework material compound anodal.
(3) assembling Na ?selenium cell
By above-mentioned preparation Xi ?micropore metal organic framework material compound positive pole with sodium negative pole assembling Na ?selenium cell, electrolyte is selected carbonic ester electrolyte (1M LiClO 4pC/EMC(mass ratio be 2:1) solution).
(4) Na ?selenium cell test
Use discharge and recharge instrument to above-mentioned Na ?selenium cell carry out constant current charge-discharge test, test voltage interval be 0.8 ?2.7V.Probe temperature is battery capacity and charging and discharging currents are all with the Mass Calculation of selenium.Described Na ?selenium cell first circle discharge capacity under 0.1C multiplying power in above-mentioned voltage range be 760mA h g ?1, first circle charging capacity is 450mA h g ?1, the second circle starts, and capacity is stabilized in 420mA h g gradually ?1left and right.Described Na ?selenium cell under 0.1C multiplying power through 50 circles circulations, capacity still remains on 390mA h g ?1left and right.
Comparative example 4.1
Other condition is identical with embodiment 4, difference be only preparation Xi ?the Coordination Polymers carrier that adopts during carbon complex be that average pore size is the mesoporous carrier of 10nm.Prepared Na ?selenium cell after the test of same method of testing, first circle discharge capacity is 500mA h g ?1, the second circle starts, and capacity is stabilized in 310mAh g gradually ?1left and right.
In sum, Na of the present invention ?selenium cell can comprise room temperature compared with large-temperature range in possess high circulation volume, excellent room temperature cyclical stability and good high rate performance, its chief component Xi ?the preparation method of porous carrier compound positive pole simple, raw material is easy to get, suitable for mass production.Although the cost of selenium is higher, by selenium and sodium assembled battery with low cost, can effectively reduce the manufacturing cost of battery.Simultaneously, with reported at present Li ?selenium cell compare, described room temperature Na ?selenium cell there is the better economy of energy (cost of sodium is significantly lower than lithium), be more suitable for heavy industrialization, and can effectively alleviate the demand of current secondary battery industry to lithium resource.Thereby Na of the present invention ?selenium cell be expected to as a kind of novel high-energy-density energy storage device, and have a good application prospect.

Claims (10)

1. a sodium ?selenium cell, comprise sodium metal as negative pole, as anodal Xi ?porous carrier composite electrode and organic electrolyte, described Xi ?porous carrier composite electrode You Xi ?porous carrier composite positive pole and conductive additive, binding agent and solvent prepare, it is characterized in that described Xi ?porous carrier compound positive electrode by the preparation of selenium and porous carrier and obtain, described selenium is dispersed in the micropore canals of described porous carrier with the form of chain molecule; The quality percentage composition of described selenium in described porous carrier be 20 ?93%.
Preferably, described organic electrolyte is carbonic ester electrolyte or ether electrolyte, concentration be 0.1 ?2M, preferably 0.5 ?1.5M;
Preferably, in described carbonic ester electrolyte, solvent is selected from least one in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate and propene carbonate, and solute is selected from least one in sodium hexafluoro phosphate, sodium perchlorate, sodium iodide and two (trimethyl fluoride sulfonyl) imines sodium;
Preferably, in described ether electrolyte, solvent be selected from 1,3 ?at least one in dioxolanes, glycol dimethyl ether and TRIGLYME, solute is selected from least one in sodium hexafluoro phosphate, sodium perchlorate, sodium iodide and two (trimethyl fluoride sulfonyl) imines sodium.
Na according to claim 1 ?selenium cell, it is characterized in that: described porous carrier is selected from one or more in carbon porous carrier and non-carbon porous carrier;
The specific area of described porous carrier be 200 ?4500m 2g ?1, pore volume be 0.1 ?3.0cm 3g ?1, average pore size be 0.2 ?2nm.
Na according to claim 2 ?selenium cell, it is characterized in that: described non-carbon porous carrier is specifically selected from one or more in micropore conducting polymer, micropore metal, micropore metal oxide, micropore semiconductive ceramic, microporous coordination polymer and micropore metal-organic framework material;
Wherein, described micropore conducting polymer is selected from one or more in polyaniline, polyacetylene, polyhenylene, polypyrrole and polythiophene;
Described micropore metal is selected from one or more in micropore gold, micropore platinum, micropore aluminium, micropore ruthenium, microporous nickel and micropore titanium;
Described micropore metal oxide is selected from one or more in micropore tri-iron tetroxide, micropore titanium dioxide and micropore ruthenium-oxide;
Described micropore semiconductive ceramic is selected from one or more in micro-pore silicon carbide and micropore zinc oxide;
Described Wei Kong Jin Shu ?organic backbone Coordination Polymers be selected from MIL ?100 (Cr), MIL ?101 (Cr) and MOF ?one or more in 5; Described non-carbon micro porous molecular sieve is selected from one or more in 3A molecular sieve, 5A molecular sieve, 10X molecular sieve and 13X molecular sieve.
Na according to claim 2 ?selenium cell, wherein said Xi ?the preparation method of porous carrier composite positive pole under inert gas shielding, be warming up to after comprising the steps: selenium and described porous carrier to mix insulation, then stop heating being cooled to room temperature, obtain described Xi ?porous carrier compound.
Na according to claim 4 ?selenium cell, it is characterized in that: the mass ratio of described selenium and described porous carrier be 0.25 ?13:1, preferably 0.5 ?10:1, more preferably 0.5 ?4:1;
Described inert gas is the gas that nitrogen, argon gas, helium etc. do not react with selenium or porous carrier;
In described heating step, heating rate is min ?1;
In described incubation step, the time be 2 ?20 hours.
Na according to claim 1 ?selenium cell, wherein said Xi ?the preparation method of porous carrier composite electrode comprise by described Xi ?porous carrier compound positive electrode, through slurrying, smear, dry technological process, make.
Xi according to claim 6 ?porous carrier composite electrode, it is characterized in that: preferably, described conductive additive be carbon black, Super ?one or more in P, Ketjen black;
Preferably, described binding agent and coordinative solvent are one or more in Kynoar (PVDF) (take N ?methyl pyrrolidone (NMP) be solvent) or polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC), butadiene-styrene rubber/sodium carboxymethylcellulose, sodium alginate (SA), gelatin (all take water as solvent); Preferably, described binding agent is sodium alginate, and preferably described sodium alginate is used with the form of the aqueous solution.
Na according to claim 3 ?selenium cell, it is characterized in that: described non-carbon porous carrier be selected from micropore metal oxide or Wei Kong Jin Shu ?organic backbone Coordination Polymers;
Wherein said micropore metal oxide is selected from one or more in micropore tri-iron tetroxide, micropore titanium dioxide and micropore ruthenium-oxide.
Na claimed in claim 1 ?selenium cell, wherein
Described organic electrolyte is preferably carbonic ester electrolyte or ether electrolyte, concentration be 0.1 ?2M, preferably 0.5 ?1.5M;
Preferably, in described carbonic ester electrolyte, solvent is selected from least one in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate and propene carbonate, and solute is selected from least one in sodium hexafluoro phosphate, sodium perchlorate, sodium iodide and two (trimethyl fluoride sulfonyl) imines sodium;
Preferably, in described ether electrolyte, solvent be selected from 1,3 ?at least one in dioxolanes, glycol dimethyl ether and TRIGLYME, solute is selected from least one in sodium hexafluoro phosphate, sodium perchlorate, sodium iodide and two (trimethyl fluoride sulfonyl) imines sodium.
Described in claim 9 Na ?the application of selenium cell in preparing high-energy-density type energy storage device.
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