CN103187559B - A kind of selenium-porous carrier compound, Preparation Method And The Use - Google Patents
A kind of selenium-porous carrier compound, Preparation Method And The Use Download PDFInfo
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- CN103187559B CN103187559B CN201310067181.5A CN201310067181A CN103187559B CN 103187559 B CN103187559 B CN 103187559B CN 201310067181 A CN201310067181 A CN 201310067181A CN 103187559 B CN103187559 B CN 103187559B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of lithium-selenium cell and preparation method thereof.This lithium-selenium cell comprises lithium anode, selenium-porous carrier compound positive pole and organic electrolyte.Described selenium-porous carrier compound positive pole mixes rear heating by a certain percentage by selenium and porous carrier and makes, and selenium is dispersed in the micropore canals of porous carrier with short chain shape molecular forms.Described porous carrier comprises carbon porous carrier, non-carbon porous carrier and composition thereof.Lithium-selenium cell provided by the invention can comprise room temperature compared with keeping high circulation volume, excellent stable circulation and good high magnification (high current density discharge and recharge) performance in large-temperature range, the preparation method of its chief component selenium-porous carrier compound positive pole is simple, raw material is easy to get, suitable for mass production, possesses very high practicality.
Description
Technical field
The invention belongs to field of electrochemical power source, be specifically related to a kind of selenium-porous carrier compound, its preparation method, selenium-porous carrier composite positive pole and preparation method thereof, the preparation method of the positive pole containing this compound, uses the application in the Novel lithium-selenium cell of this positive pole and high volume energy density type energy storage device thereof.
Background technology
Lithium-selenium cell refers to and adopts elemental selenium or selenium-containing compound to be positive pole, and lithium metal is negative pole, is realized a metalloid lithium secondary battery of conversion mutually between chemical energy and electric energy by the chemical reaction between selenium and lithium.Elemental selenium, because of its two electron reactions in electrochemical reaction process, high lithiumation current potential and high density, have very high theoretical volume specific capacity, adapts to the development trend at present to the exclusive mobile device of volume.In addition, compare most positive electrode, selenium is high as its conductivity of semiconductor, and therefore positive-active is good, and utilance can close to 100%, and selenium is in charge and discharge process stable cycle performance, and capacity attenuation is little.As can be seen here, lithium-selenium cell, as novel metal lithium secondary battery, has very important scientific research value and immeasurable application potential.
Although this novel lithium-selenium cell has, volume is little, capacity is large, the life-span is long, efficiency advantages of higher, it is a kind of secondary energy storage battery of novel high volume energy density type, but very rare to the research of lithium-selenium cell at present, the reaction mechanism in charge and discharge process of selenium as electrode material activity material is still not clear.Not long ago, the people such as Amine (J.Am.Chem.Soc.2012,134,4505-4508) have carried out exploratory research work to the discharge and recharge reaction mechanism of selenium positive pole in lithium-selenium cell, lithium-the selenium cell of its exploitation adopts lithium metal to be negative pole, and the mixture of selenium and carbon nano-tube is positive pole.Due to granules of selenium size more greatly and do not carry out effective compound with conductive substrates, make the electro-chemical activity of selenium can not get effective performance, thus make lithium-selenium cell circulation volume of obtaining low.Simultaneously, due to conductive substrates to the dispersion of selenium and restriction more weak, the selenium of a part can form many selenides and be dissolved in electrolyte in cyclic process, causes the capacity of lithium-selenium cell to carry out irreversible decay occurs with circulation, has had a strong impact on the useful life of battery.Therefore, selenium and conductive substrates are carried out effective compound, selenium is limited in substrate with the form of molecule, thus preparation has the lithium-selenium cell electrode material of high volume energy density and cyclical stability, exploitation has the lithium-selenium cell of high power capacity and stable circulation performance, and the development for whole energy storage field also has great importance.
CN101794844A discloses a kind of copper fluoride-selenium nanometer composite cathode material for lithium ion battery and preparation method thereof, wherein copper fluoride and elemental selenium are formed nano composite material by the mode of laser splash, and with the negative material of this nano composite material as lithium-ion film cell, but the battery capacity of the battery obtained like this is still not ideal enough.
CN102623678A discloses the preparation method of a kind of Li-Se battery and electrode material of lithium battery, it is disclosed that and adopt the method for thermal evaporation at Grown selenium micron ball and 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, the significant wastage of selenium can be caused again, selenium is deposited on substrate surface in addition, effect instability easily comes off, the most important thing is, selenium is as anode material discharging brownout (about 0.25V) in the invention, and for electrode material of lithium battery, voltage platform can only as negative material at below 1V.Therefore, select suitable conductive substrates, selenium and conductive substrates are carried out effective compound, selenium is limited in substrate with the form of molecule simultaneously, thus preparation has the lithium-selenium cell electrode material of high volume energy density and cyclical stability, exploitation has the lithium-selenium cell of high power capacity and stable circulation performance, and the development for whole energy storage field also has great importance.
Summary of the invention
The invention provides a kind of selenium for lithium-selenium cell-porous carrier compound, described compound is prepared by selenium and porous carrier and is obtained, and described selenium is dispersed in the micropore canals of described porous carrier with the form of chain molecule; The mass percentage of described selenium in described porous carrier is 20-93%.In the composite material that the method obtains, selenium can be present in the duct of carrier with stable nano shape, and the present inventor surprisingly finds, the composite material adopting the method to obtain is as the positive electrode of lithium ion battery, can compared with keeping high circulation volume, excellent stable circulation and good high magnification (high current density discharge and recharge) performance in large-temperature range, the preparation method of its chief component selenium-porous carrier compound positive pole is simple, raw material is easy to get, suitable for mass production, possesses very high practicality.
The present invention also provides a kind of selenium-mesoporous supports composite positive pole, and described positive electrode is prepared by selenium and porous carrier and obtained, and described selenium is dispersed in the micropore canals of described porous carrier with the form of chain molecule; The mass percentage of described selenium in described porous carrier is 20-93%.
Preferably, the carrier material of microporous carrier material finger-hole footpath between 0.2-2nm described in the application.
In above-mentioned compound, described porous carrier be selected from carbon porous carrier and non-carbon porous carrier one or more;
Described carbon porous carrier is the carbon carrier or its composition that possess certain conductivity and microcellular structure;
Described non-carbon porous carrier is specifically selected from micropore conducting polymer (miroporous conductivepolymer), micropore metal (miroporous metal), micropore metal oxide (microporousmetal oxide), micropore semiconductive ceramic (miroporous semi-conductive ceramic), micropore metal-organic backbone (metal-organic framework) Coordination Polymer, 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 be selected from micropore gold, micropore platinum, micropore aluminium, micropore ruthenium, microporous nickel and micropore titanium one or more;
Described micropore metal oxide be selected from micropore tri-iron tetroxide, Microporous titania and microporous alumina ruthenium one or more;
Described micropore semiconductive ceramic be selected from micro-pore silicon carbide and microporous alumina zinc one or more;
Described micropore metal-organic backbone Coordination Polymer is selected from MIL-100 (Cr), MIL-101 (Cr) and MOF-5(is trade name, MIL is the abbreviation of Materiaux Institut Lavoisier company, and MOF is the abbreviation of metal-organic framework) at least one;
Described non-carbon micro porous molecular sieve be selected from 3A molecular sieve, 5A molecular sieve, 10X molecular sieve and 13X molecular sieve one or more.
The specific area of described porous carrier is 200-4500m
2g
-1, specifically can be preferably 300m
2g
-1, 920m
2g
-1, 4000m
2g
-1, pore volume is 0.1-3.0cm
3g
-1, specifically can be preferably 0.5cm
3g
-1, 0.2cm
3g
-1, 2cm
3g
-1, average pore size is 0.2-2nm, specifically can be preferably 0.6nm, 1.2nm, 1.6nm, or be more preferably 0.6-1.2nm.
The method of preparation provided by the invention described selenium-porous carrier compound; under inert gas shielding, be warming up to 210-270 ° of C after comprising the steps: selenium and described porous carrier to mix to be incubated; stop heating being cooled to room temperature again, obtain described selenium-porous carrier compound.
In said method, the mass ratio of described selenium and described porous carrier is 0.25-13:1, preferred 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 0.1-10 ° of Cmin
-1;
In described incubation step, the time is 2-20 hour.
The present invention also provides selenium-porous carrier composite electrode and preparation method thereof, and this selenium-porous carrier composite electrode contains described selenium-porous carrier composite positive pole, binding agent and conductive additive.Prepare described selenium-porous carrier composite electrode specifically to comprise the steps: described selenium-porous carrier compound to mix by a certain percentage with conductive additive, binding agent and solvent, namely obtain selenium-porous carrier compound positive pole through technological processes such as slurrying, smear, dryings.
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 one or more in Kynoar (PVDF) (with 1-METHYLPYRROLIDONE (NMP) for solvent) or polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC), sodium alginate (SA), gelatin (all with water for solvent).
Lithium-selenium cell provided by the invention, comprises the lithium metal as negative pole, the aforementioned selenium-porous carrier compound as positive pole and organic electrolyte.
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 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 lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4), one or more in lithium iodide (LiI) and two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI);
In described ether electrolyte, solvent is selected from least one in DOX (DOL), glycol dimethyl ether (DME) and TRIGLYME (TEGDME), and solute is selected from lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4), one or more in lithium iodide (LiI) and two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI).
The working temperature of described lithium-selenium cell is-20 ° of C-60 ° C, is specially 0 ° C-60 ° C or 30 ° C-60 ° C.
In addition, the application of lithium-selenium cell that the invention described above provides in preparation high-energy density type energy storage device, also belongs to protection scope of the present invention.
Accompanying drawing explanation
Fig. 1 is the Raman spectrogram of the described selenium-microporous carbon composite material of embodiment 1.
Fig. 2 is the cyclic voltammogram of described lithium-selenium cell in carbonic ester electrolyte of embodiment 1.
Fig. 3 is the charging and discharging curve of lithium-selenium cell in carbonic ester electrolyte under 0.1C multiplying power of embodiment 1.
Fig. 4 is the cycle performance of lithium-selenium cell in carbonic ester electrolyte under 0.1C multiplying power of embodiment 1.
Fig. 5 is the charging and discharging curve of lithium-selenium cell in carbonic ester electrolyte under different multiplying of embodiment 1.
Fig. 6 is the cycle performance of lithium-selenium cell in carbonic ester electrolyte under 1C multiplying power of embodiment 1.
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) selenium-porous carrier compound positive pole is prepared
The porous carrier adopted in experiment is microporous carbon (purchased from Kuraray company), and specific area is 920m
2g
-1, pore volume is 0.50cm
3g
-1, average pore size is 0.6nm, and in prepared selenium-microporous carbon compound, the mass fraction of selenium is 60%.
The preparation method of selenium-microporous carbon compound is as follows:
(1) ratio of selenium and microporous carbon 3:2 is in mass ratio weighed and Homogeneous phase mixing;
(2) by the mixture of selenium and microporous carbon with 0.2 ° of C min
-1heating rate be heated to 215 ° of C and maintain heating 12h, selenium is fully distributed in microporous carbon;
(3) stop heating and falling back room temperature, obtain selenium-microporous carbon compound.
Fig. 1 is the Raman spectrogram of described selenium-microporous carbon composite material, can 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) selenium-porous carrier compound positive pole is prepared
By the selenium of above-mentioned preparation-microporous carbon compound and carbon black, binding agent polyvinylidene fluoride in mass ratio 9:0.5:0.5 mix, and add solvent N-methyl pyrilidone, namely obtain selenium-microporous carbon compound positive pole through technological processes such as slurrying, smear, dryings.
(3) lithium-selenium cell is assembled
The selenium of above-mentioned preparation-microporous carbon compound positive pole is assembled lithium-selenium cell with cathode of lithium, and carbonic ester electrolyte (the EC/DMC(mass ratio of 1M LiTFSI is 1:1) solution selected by electrolyte).
(4) lithium-selenium cell test
Use discharge and recharge instrument to carry out constant current charge-discharge test to above-mentioned lithium-selenium cell, use electrochemical workstation to carry out cyclic voltammetry to above-mentioned lithium-selenium cell, test voltage interval is 1-3V.Probe temperature is 0 ° of C, and battery capacity and charging and discharging currents are all with the Mass Calculation of selenium.Fig. 2 is the cyclic voltammogram of described lithium-selenium cell in carbonic ester electrolyte, and a reduction peak (~ 1.8V) appears in described lithium-selenium cell in cathodic process, a corresponding appearance oxidation peak (~ 1.9V) in anodic process.Fig. 3 is that described lithium-selenium cell 0.1C(in carbonic ester electrolyte is equivalent to 68mA g
-1) charging and discharging curve under multiplying power.The charging and discharging curve of described lithium-selenium cell in above-mentioned voltage range only has a platform, and its first circle discharge capacity is 1020mA h g
-1, first circle charging capacity is 710mA h g
-1, the second circle starts, and capacity is stabilized in 680mA h g gradually
-1left and right.Fig. 4 is the cycle performance of described lithium-selenium cell in carbonic ester electrolyte under 0.1C multiplying power.Described lithium-selenium cell is through 20 circle circulations, and capacity still remains on 675mA h g
-1left and right.Fig. 5 is the charging and discharging curve of described lithium-selenium cell in carbonic ester electrolyte under different multiplying.The charging and discharging curve of lithium-selenium cell under each multiplying power is stablized, and is equivalent to 6800mA g when multiplying power is promoted to 10C(
-1) time, its capacity still remains on 300mA h g
-1left and right.Fig. 6 is the cycle performance of described lithium-selenium cell in carbonic ester electrolyte under 1C multiplying power.After 20 circle circulations, the discharge capacity of described lithium-selenium cell still remains on 550mA h g
-1left and right, has excellent capability retention and good high rate capability.
Comparative example 1.1
Other condition is identical with embodiment 1, when difference is only to prepare selenium-porous carrier compound positive pole, sodium carboxymethylcellulose selected by binding agent, and water selected by solvent, and the first circle discharge capacity recorded under 0.1C multiplying power after being assembled into lithium-selenium cell is 1080mA h g
-1, first circle charging capacity is 730mAh g
-1, the second circle starts, and capacity is stabilized in 695mA h g gradually
-1left and right.Through 20 circle circulations, the capacity of described lithium-selenium cell still remains on 685mA h g
-1left and right.The capacity of described lithium-selenium cell under 10C current density still remains on 310mA h g
-1, the discharge capacity after 100 circles that circulate under 1C multiplying power still remains on 600mA h g
-1left and right, has excellent capability retention and good high rate capability.
Comparative example 1.2
Other condition is identical with embodiment 1, and difference is only that in selenium microporous carrier material, carrier employing average pore size is the porous carbon materials of about 2 microns, and the first circle charging capacity recorded after being assembled into lithium-selenium cell is 410mA h g
-1, the second circle starts, and capacity is stabilized in 330mA h g gradually
-1left and right.
Embodiment 2
(1) selenium-porous carrier compound positive pole is prepared
The porous carrier adopted in experiment is micropore tri-iron tetroxide (purchased from Sigma-Aldrich company), and specific area is 300m
2g
-1, pore volume is 0.2cm
3g
-1, average pore size is 1.6nm, and in prepared selenium-micropore ferroferric oxide compound, the mass fraction of selenium is 30%.
The preparation method of selenium-micropore ferroferric oxide compound is as follows:
(1) ratio of selenium and micropore tri-iron tetroxide 3:7 is in mass ratio weighed and Homogeneous phase mixing;
(2) by the mixture of selenium and micropore tri-iron tetroxide with 3 ° of C min
-1heating rate be heated to 230 ° of C and maintain heating 5h, make selenium fully be distributed in micropore tri-iron tetroxide;
(3) stop heating and falling back room temperature, obtain selenium-micropore ferroferric oxide compound.
(2) selenium-porous carrier compound positive pole is prepared
By the selenium of above-mentioned preparation-micropore ferroferric oxide compound and Super-P, binding agent gelatin and water in mass ratio 8:1:1 mix, namely obtain selenium-micropore ferroferric oxide compound positive pole through technological processes such as slurrying, smear, dryings.
(3) lithium-selenium cell is assembled
The selenium of above-mentioned preparation-micropore ferroferric oxide compound positive pole is assembled lithium-selenium cell with cathode of lithium, and ether electrolyte (0.5M LiClO selected by electrolyte
4dOL/DME(mass ratio be 1:1) solution).
(4) lithium-selenium cell test
Use discharge and recharge instrument to carry out constant current charge-discharge test to above-mentioned lithium-selenium cell, test voltage interval is 1-2.7V.Probe temperature is 30 ° of C, and battery capacity and charging and discharging currents are all with the Mass Calculation of selenium.The first circle discharge capacity of described lithium-selenium cell in above-mentioned voltage range under 0.1C multiplying power is 1230mA hg
-1, first circle charging capacity is 700mA h g
-1, the second circle starts, and capacity is stabilized in 690mA hg gradually
-1left and right.Described lithium-selenium cell is through 100 circle circulations under 0.1C multiplying power, and capacity still remains on 680mA h g
-1left and right.Fig. 6 is the cycle performance of described lithium-selenium cell in ether electrolyte under 1C multiplying power.After 50 circle circulations, the discharge capacity of described lithium-selenium cell still remains on 600mA h g
-1left and right, has excellent capability retention and good high rate capability.
Embodiment 3
(1) selenium-porous carrier compound positive pole is prepared
The porous carrier adopted in experiment is micropore metal-organic backbone Coordination Polymer (MIL-100 (Cr) is the Coordination Polymer that chromium and trimesic acid are formed, purchased from Materiaux InstitutLavoisier company), and specific area is 4000m
2g
-1, pore volume is 2cm
3g
-1, average pore size is 1.2nm, and in prepared selenium-micropore metal organic framework material compound, the mass fraction of selenium is 80%.
The preparation method of selenium-micropore metal organic framework material compound is as follows:
(1) ratio of selenium and micropore metal organic framework material 4:1 is in mass ratio weighed and Homogeneous phase mixing;
(2) by the mixture of selenium and micropore metal organic framework material with 8 ° of C min
-1heating rate be heated to 265 ° of C and maintain heating 18h, make selenium fully be distributed in micropore metal organic framework material;
(3) stop heating and falling back room temperature, obtain selenium-micropore metal organic framework material compound.
(2) selenium-porous carrier compound positive pole is prepared
By the selenium of above-mentioned preparation-micropore metal organic framework material compound and Ketjen black, binding agent sodium carboxymethylcellulose and water in mass ratio 7:2:1 mix, namely obtain selenium-micropore metal organic framework material compound positive pole through technological processes such as slurrying, smear, dryings.
(3) lithium-selenium cell is assembled
The selenium of above-mentioned preparation-micropore metal organic framework material compound positive pole is assembled lithium-selenium cell with cathode of lithium, and carbonic ester electrolyte (1M LiClO selected by electrolyte
4pC/EMC(mass ratio be 2:1) solution).
(4) lithium-selenium cell test
Use discharge and recharge instrument to carry out constant current charge-discharge test to above-mentioned lithium-selenium cell, test voltage interval is 1-3V.Probe temperature is 60 ° of C, and battery capacity and charging and discharging currents are all with the Mass Calculation of selenium.The first circle discharge capacity of described lithium-selenium cell in above-mentioned voltage range under 0.1C multiplying power is 760mA h g
-1, first circle charging capacity is 540mA h g
-1, the second circle starts, and capacity is stabilized in 520mA h g gradually
-1left and right.Described lithium-selenium cell is through 50 circle circulations under 0.1C multiplying power, and capacity still remains on 500mAh g
-1left and right.Described lithium-selenium cell is under 1C multiplying power after 200 circle circulations, and discharge capacity still remains on 490mA h g
-1left and right, has excellent capability retention and good high rate capability.
Embodiment 4
Other condition is identical with embodiment 4, and difference is only that porous carrier used uses the mesoporous supports that average pore size is 10nm instead.Obtained lithium-selenium cell is after the test of same method of testing, and first circle discharge capacity is 500mA h g
-1, the second circle starts, and capacity is stabilized in 440mA h g gradually
-1left and right.
In sum, lithium-selenium cell of the present invention can comprise room temperature compared with possessing high circulation volume in large-temperature range, excellent room temperature cycles stability and good high rate performance, the preparation method of its chief component selenium-porous carrier compound positive pole is simple, raw material is easy to get, suitable for mass production, thus lithium-selenium cell of the present invention is expected to as a kind of novel high-energy-density energy storage device, and has a good application prospect.
Foregoing is only the preferred embodiments of the present invention; not for limiting embodiment of the present invention; those of ordinary skill in the art are according to central scope of the present invention and spirit; can carry out corresponding flexible or amendment very easily, therefore protection scope of the present invention should be as the criterion with the protection range required by claims.
Claims (1)
1. lithium-selenium cell, it prepares as follows,
(1) selenium-porous carrier compound positive pole is prepared
The porous carrier adopted is the micropore tri-iron tetroxide purchased from Sigma-Aldrich company, and specific area is 300m
2g
-1, pore volume is 0.2cm
3g
-1, average pore size is 1.6nm, and in prepared selenium-micropore ferroferric oxide compound, the mass fraction of selenium is 30%,
The preparation method of selenium-micropore ferroferric oxide compound is as follows:
(1) ratio of selenium and micropore tri-iron tetroxide 3:7 is in mass ratio weighed and Homogeneous phase mixing;
(2) by the mixture of selenium and micropore tri-iron tetroxide with 3 DEG C of min
-1heating rate be heated to 230 DEG C and maintain heating 5h, make selenium fully be distributed in micropore tri-iron tetroxide;
(3) stop heating and falling back room temperature, obtain selenium-micropore ferroferric oxide compound;
(2) selenium-porous carrier compound positive pole is prepared
By the selenium of above-mentioned preparation-micropore ferroferric oxide compound and Super-P, binding agent gelatin and water in mass ratio 8:1:1 mix, obtain selenium-micropore ferroferric oxide compound positive pole through slurrying, smear, drying;
(3) lithium-selenium cell is assembled
The selenium of above-mentioned preparation-micropore ferroferric oxide compound positive pole is assembled lithium-selenium cell with cathode of lithium, and 0.5M LiClO selected by electrolyte
4dOL/DME solution, and wherein the mass ratio of DOL and DME is 1:1.
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| US10734638B2 (en) | 2015-09-22 | 2020-08-04 | Ii-Vi Delaware, Inc. | Immobilized selenium, a method of making, and uses of immobilized selenium in a rechargeable battery |
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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 |
| KR102471212B1 (en) * | 2016-02-17 | 2022-11-28 | 투-식스 인코포레이티드 | The immobilization selenium, and the use of the immobilization selenium in the manufacturing method thereof and recharging battery |
| CN106784660B (en) * | 2016-12-02 | 2019-04-05 | 吉林大学 | Se-TiO of the nickel foam as interlayer2/ NFF lithium selenium secondary cell and preparation method thereof |
| 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 |
| CN107748229B (en) * | 2017-10-16 | 2019-11-12 | 任宇齐 | A kind of mixed feed additive sodium selenite carries the detection method of quality |
| CN108878817A (en) * | 2018-06-15 | 2018-11-23 | 华南理工大学 | Reduce lithium selenium cell positive electrode, electrode slice and button cell that more selenides are lost |
| CN109360971B (en) * | 2018-11-26 | 2020-04-14 | 重庆文理学院 | Preparation method of microspherical manganese selenide/carbon composite material |
| CN111193028B (en) * | 2020-01-08 | 2022-11-11 | 九江学院 | Preparation method of Fe-CrSe/C composite electrode material with nano structure |
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