CN103178246A - Selenium-mesoporous carrier compound, as well as preparation method and application thereof - Google Patents
Selenium-mesoporous carrier compound, as well as preparation method and application thereof Download PDFInfo
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- CN103178246A CN103178246A CN2013100668704A CN201310066870A CN103178246A CN 103178246 A CN103178246 A CN 103178246A CN 2013100668704 A CN2013100668704 A CN 2013100668704A CN 201310066870 A CN201310066870 A CN 201310066870A CN 103178246 A CN103178246 A CN 103178246A
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Abstract
The invention discloses a lithium-selenium battery and a preparation method of the lithium-selenium battery. The lithium-selenium battery comprises a metal lithium cathode, a selenium-mesoporous carrier compound anode and an organic electrolyte, wherein the selenium-mesoporous carrier compound anode is formed by mixing selenium with a mesoporous carrier in a certain proportion and then heating a mixture; the selenium is uniformly dispersed in a mesoporous channel of the mesoporous carrier in an annular selenium molecular form and/or an amorphous chain selenium molecular form; and the mesoporous carrier comprises a carbon mesoporous carrier, a non-carbon mesoporous carrier and compositions thereof. The lithium-selenium battery provided by the invention has the advantages of small size, high capacity, long service life, high efficiency, simplicity in reaction platform and the like, and is a novel secondary energy storage battery with high volume energy density. The preparation method of the main component namely the selenium-mesoporous carrier compound anode of the battery is simple. Raw materials are easily available. The lithium-selenium battery is suitable for large-scale production and high in practicability.
Description
Technical field
The invention belongs to field of electrochemical power source, be specifically related to a kind of selenium-mesoporous carrier complexes, its preparation method, selenium-mesoporous carrier composite positive pole and preparation method thereof, the preparation method who contains the positive pole of this compound uses the application in this anodal Novel lithium-selenium cell and high volume energy density type energy storage device thereof.
Background technology
Lithium-selenium cell refers to adopt simple substance selenium or selenium-containing compound for anodal, and lithium metal is negative pole, realizes a metalloid lithium secondary battery of mutually changing between chemical energy and electric energy by the chemical reaction between selenium and lithium.Simple substance selenium, two electron reaction mechanism and high density because of it in electrochemical reaction process have very high theoretical volume specific capacity, adapt to present development trend to the strict mobile device of volume restrictions.In addition, compare most positive electrodes, selenium is high as its conductivity of semiconductor, therefore anodal active good, utilance can be near 100%, and selenium form in charge and discharge process substantially do not form the many plasma seleniums that are dissolved in electrolyte, so stable cycle performance, capacity attenuation is little.This shows, lithium-selenium cell has very important scientific research and is worth and immeasurable application potential as the novel metal lithium secondary battery.
Volume is little, capacity is large, the life-span is long, the efficient advantages of higher although this novel lithium-selenium cell has, it is a kind of secondary energy storage battery of novel high volume energy density type, but at present very rare to the research of lithium-selenium cell, the reaction mechanism in charge and discharge process of selenium as the electrode material activity material is still not clear.Therefore develop the lithium of simple, steady operation-selenium cell electrode material and with battery assembly method, significant for further investigation selenium electrode electro Chemical reactivity worth and reaction mechanism, also will play a great role to the development in whole mobile energy storage field.Not long ago, the people such as Amine (J.Am.Chem.Soc.2012,134,4505-4508) lithium-selenium cell has been made premonitory work, the reaction mechanism of selenium is made certain exploration, but because it adopts carbon nano-tube as conductive substrates, selenium-the carbon mix that makes is as positive pole, selenium exists with the form of bulk, and a little less than the restriction of substrate to selenium, thereby the electro-chemical activity of selenium can not get effective performance, react unstable, lithium-selenium cell circulation volume is low, and the discharge capacity decay is fast, and battery life is limited.Patent CN101794877A discloses a kind of copper fluoride-selenium nanometer composite cathode material for lithium ion battery and preparation method thereof, wherein the mode by laser splash forms nano composite material with copper fluoride and simple substance selenium, and with the negative material of this nano composite material as lithium-ion film cell, but, the preparation method here is complicated, be only applicable to special purpose and be not suitable for large-scale application, and the battery capacity of the battery that obtains like this is on the low side, only have 310mA h/g.patent CN102623678A discloses the preparation method of a kind of Li-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, selenium is as anode material discharging brownout (approximately 0.25V) in this invention, and for electrode material of lithium battery, voltage platform can only be as negative material below 1V.Therefore, select suitable conductive substrates, carry out selenium and conductive substrates effectively compound, simultaneously the form of selenium with molecule is limited in substrate, thereby preparation has the lithium of high volume energy density and cyclical stability-selenium cell electrode material, lithium-selenium cell that exploitation has high power capacity and stable circulation performance also has great importance for the development in whole energy storage field.
Summary of the invention
The invention provides a kind of selenium-mesoporous carrier complexes, described compound is prepared and is got by selenium and mesoporous carrier, and described selenium is dispersed in the mesopore orbit of described mesoporous carrier with the form of single ring-type selenium molecule and/or amorphous chain selenium molecule; The quality percentage composition of described selenium in described mesoporous carrier is 10-90%.In the composite material that the method obtains, selenium can be present in stable molecular dimension 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 lithium ion battery, can keep high circulation volume, excellent stable circulation, single discharge platform stably, the preparation method of its chief component selenium-mesoporous carrier complexes positive pole is simple, and raw material is easy to get, suitable for mass production possesses very high practicality.
The present invention also provides a kind of selenium-mesoporous carrier composite positive pole, described positive electrode is prepared and is got by selenium and mesoporous carrier, and described selenium is dispersed in the mesopore orbit of described mesoporous carrier with the form of single ring-type selenium molecule and/or amorphous chain selenium molecule; The quality percentage composition of described selenium in described mesoporous carrier is 10-90%.
Preferably, the mesoporous carrier material finger-hole footpath described in the present invention is at 2-50nm, preferably at 2-10nm, and the carrier material of 2-5nm more preferably.
In above-mentioned positive electrode, described mesoporous carrier is selected from one or more in the mesoporous carrier of carbon and the mesoporous carrier of non-carbon;
The mesoporous carrier of described carbon is carbon carrier or its composition that possesses certain conductivity and meso-hole structure;
The mesoporous carrier of described non-carbon specifically is selected from one or more in mesoporous metal, mesopore metal oxide, mesoporous semiconductive ceramic, mesopore molecular sieve and mesoporous phosphate material;
Wherein, described mesoporous metal is selected from one or more in mesoporous gold, mesoporous platinum, mesoporous aluminium, mesoporous nickel and mesoporous titanium;
Described mesopore metal oxide is selected from one or more in mesoporous di-iron trioxide, mesoporous ferriferrous oxide, mesoporous TiO 2 and mesoporous ruthenium-oxide;
Described mesoporous semiconductive ceramic is selected from one or more in mesoporous silicon carbide and mesoporous zinc oxide;
Described mesopore molecular sieve is selected from one or more in MCM series and SBA series mesopore molecular sieve.
Described mesoporous phosphate material is selected from one or more in mesoporous aluminum phosphate, mesoporous titanium phosphate, mesoporous vanadium phosphate, mesoporous ferric phosphate, mesoporous trbasic zinc phosphate.
The method of the described selenium of preparation provided by the invention-mesoporous carrier composite positive pole, comprise the steps: after selenium and described mesoporous carrier mixing, be warming up to 220-300 ° of C insulation in the constant volume reactor of inert atmosphere being full of, stopped heating is cooled to room temperature again, obtains described selenium-mesoporous carrier complexes.
In said method, the specific surface of described mesoporous carrier is 200-3000m
2g
-1, pore volume is 0.2-10.0cm
3g
-1, average pore size is 2-50nm, preferably, described pore volume is 0.5-5.0cm
3g
-1, more preferably, described pore volume is 0.8-3.0cm
3g
-1Also preferably, described average pore size is 2-10nm, more preferably 2-5nm.
Preferably, the mass ratio of described selenium and described mesoporous carrier is 0.1:1～9:1, and preferred 0.25:1～4:1 also is preferably 1:1～3:1.
Preferably, described inert atmosphere is one or more inert gas atmospheres such as nitrogen, argon gas.
Preferably, in described heating step, heating rate is 1-10 ° of C min
-1
Preferably, in described incubation step, the time is 10-24 hour.
The present invention also provides selenium-mesoporous carrier complexes electrode and preparation method thereof, and this selenium-mesoporous carrier complexes electrode contains described selenium-mesoporous carrier composite positive pole, binding agent and conductive additive.Prepare described selenium-mesoporous carrier complexes electrode and specifically comprise the steps: described selenium-mesoporous carrier complexes is mixed by a certain percentage with conductive additive, binding agent and solvent, namely obtain selenium-mesoporous carrier complexes through technological processes such as slurrying, smear, dryings anodal.
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) (take 1-METHYLPYRROLIDONE (NMP) as solvent) or polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC), sodium alginate (SA), gelatin (all take water as solvent).
Lithium-selenium cell provided by the invention comprises lithium metal as negative pole, as anodal above-mentioned selenium-mesoporous carrier complexes electrode 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 one or more 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) and two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI) in one or more.
In described ether electrolyte, solvent is selected from one or more in DOX (DOL), glycol dimethyl ether (DME) and TRIGLYME (TEGDME), and solute is selected from lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4) and two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI) in one or more.
In addition, the application of lithium-selenium cell that the invention described above provides in the high volume energy density type energy storage device of preparation also belongs to protection scope of the present invention.
Description of drawings
Fig. 1 is that the selenium-mesoporous carbon carrier complexes of embodiment 1 amplifies the transmission electron microscope photo of 48000 times.
Fig. 2 is lithium-selenium cell charging and discharging curve under the 0.1C multiplying power in carbonic ester electrolyte of embodiment 1.
Fig. 3 is lithium-selenium cell cycle performance under the 0.1C multiplying power in carbonic ester electrolyte of embodiment 1.
Fig. 4 is that the selenium-mesoporous carbon carrier complexes of embodiment 1 is before and after circulation and the Raman spectrum of block selenium.
Fig. 5 is lithium-selenium cell charging and discharging curve under the 0.1C multiplying power in carbonic ester electrolyte of embodiment 2.
Fig. 6 is lithium-selenium cell charging and discharging curve under the 0.1C multiplying power in carbonic ester electrolyte of embodiment 3.
Fig. 7 is lithium-selenium cell cycle performance under the 0.1C multiplying power in carbonic ester electrolyte of embodiment 3.
Fig. 8 is lithium-selenium cell cycle performance under the 0.1C multiplying power in carbonic ester electrolyte of embodiment 4.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
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) preparation selenium-mesoporous carrier complexes
The mesoporous carrier that adopts in experiment is mesoporous carbon (available from Nanjing Xian Feng Nono-material Science ﹠ Technology Ltd.), and specific area is 612.3m
2g
-1, pore volume is 0.697cm
3g
-1, average pore size is 4.3nm, in prepared selenium-mesoporous carbon complex, the mass fraction of selenium is 50%.
The preparation method of selenium-mesoporous carbon complex is as follows:
(1) with selenium and mesoporous carbon in mass ratio the ratio of 1:1 weigh and evenly mix;
(2) with the mixture of selenium and mesoporous carbon in being full of the constant volume reactor of argon gas with 5 ° of C min
-1Heating rate be heated to 260 ° of C and keep the heating 12h, make selenium fully be distributed in mesoporous carbon;
(3) stopped heating and fall back room temperature obtains selenium-mesoporous carbon complex.
Can know from the transmission electron microscope photo of Fig. 1 and see that selenium is present in the mesopore orbit of mesoporous carrier fully, not remain in mesoporous carrier surface, thereby mesoporous carrier has good restriction to the selenium molecule, selenium forms is highly stable.
(2) preparation selenium-mesoporous carrier complexes is anodal
With the selenium-mesoporous carbon complex of above-mentioned preparation with Super-P, binding agent sodium alginate with water mixes by a certain percentage, it is anodal namely to obtain selenium-mesoporous carbon complex through technological processes such as slurrying, smear, dryings.
(3) assembling lithium-selenium cell
The selenium of above-mentioned preparation-mesoporous carbon complex positive pole is assembled lithium-selenium cell with cathode of lithium, and electrolyte is selected carbonic ester electrolyte (1M LiPF
6The PC/EC(volume ratio be 1:1) solution).
(4) lithium-selenium cell test
Use discharges and recharges instrument above-mentioned lithium-selenium cell is carried out constant current charge-discharge test, uses electrochemical workstation to carry out cyclic voltammetry to above-mentioned lithium-selenium cell, and the test voltage interval is 1.0-3.0V, and probe temperature is 25 ° of C.Battery capacity and charging and discharging currents are all with the Mass Calculation of simple substance selenium.Fig. 2 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 first circle discharge capacity of described lithium-selenium cell in above-mentioned voltage range is 932mA h g
-1, the first circle charging capacity is 696mA h g
-1, the second circle beginning, capacity is stabilized in 675mA h g gradually
-1The left and right, cyclic curve is stable, coulombic efficiency approximately 100%, discharge platform is single platform, discharge voltage is near 2V.Fig. 3 is described lithium-selenium cell cycle performance under the 0.1C multiplying power in carbonic ester electrolyte.Described lithium-selenium cell is through 30 circle circulations, and capacity still remains on 670mA h g
-1The left and right has good capability retention and coulombic efficiency.Fig. 4 is that described selenium-mesoporous carbon complex is at the Raman spectrum that discharges and recharges front and back and block selenium.As seen selenium exists with single ring-type selenium molecule before discharging and recharging, and after the process circulation, selenium changes the form of amorphous chain selenium molecule into.This reaction formation from the body phase selenium of the bulk of previous report is different.
Comparative Examples 1.1
Other condition is identical with embodiment 1, and difference only is in the mesoporous carrier material of selenium that it is the about porous carbon materials of 2 microns that carrier adopts average pore size, and the first circle charging capacity that records after being assembled into lithium-selenium cell is 300mA h g
-1, the second circle beginning, capacity is stabilized in 100mA h g gradually
-1The left and right.
Embodiment 2
Other condition is identical with embodiment 1, and difference only is that the binding agent that uses in step (two) is not sodium alginate (with water as solvent), but Kynoar (PVDF) (take 1-METHYLPYRROLIDONE (NMP) as solvent).The lithium of assembling-selenium cell use discharges and recharges instrument above-mentioned lithium-selenium cell is carried out the constant current charge-discharge test, and the test voltage scope is 1.0-3.0V, and probe temperature is 25 ° of C.Battery capacity and charging and discharging currents are all with the Mass Calculation of simple substance selenium.Fig. 5 is that this routine described lithium-selenium cell 0.1C(in carbonic ester electrolyte is equivalent to 68mA g
-1) charging and discharging curve under multiplying power.The first circle discharge capacity of described lithium-selenium cell in above-mentioned voltage range is 932mA h g
-1, the first circle charging capacity is 578mA h g
-1, second the circle begin to circulate 50 the circle after, discharge capacity still remains on 550mA h g
-1Above, capability retention and good coulombic efficiency are preferably arranged, its discharge voltage is still compared embodiment, capacity and less efficient equally near 2V.
Embodiment 3
(1) preparation mesoporous carbon carrier
The mesoporous carrier that adopts in experiment is mesoporous carbon, and specific area is 1789m
2g
-1, pore volume is 2.37cm
3g
-1, average pore size is 3.8nm.
The preparation method of mesoporous carbon is as follows:
1.25g sucrose is dissolved in the aqueous solution that 5mL contains the 0.14g concentrated sulfuric acid, add again the silica-based molecular sieve of 1.0g nano-pore (available from Shanghai carbon connection Environmental Protection Technology Co., Ltd), then ultrasonic dispersion 1h is heated to 100 ° of C and keeps heating 12h, then is heated to 160 ° of C and keeps heating 12h.Add afterwards 0.8g sucrose, the 0.09g concentrated sulfuric acid and 5mL water, Repeat-heating to 100 ° C also keeps heating 12h, then is heated to 160 ° of C and keeps heating 12h.With product under argon gas atmosphere with 10 ° of C min
-1Heating rate be heated to 900 ° of C and keep the heating 5h make the organic substance carbonization, at last product is stirred 4h and remove silicon in diluted hydrofluoric acid, obtain the mesoporous carbon carrier.
(2) preparation selenium-mesoporous carrier complexes
In experiment in prepared selenium-mesoporous carbon complex the mass fraction of selenium be 70%.
The preparation method of selenium-mesoporous carbon complex is as follows:
(1) with selenium and mesoporous carbon in mass ratio the ratio of 7:3 weigh and evenly mix;
(2) with the mixture of selenium and mesoporous carbon in being full of the constant volume reactor of argon gas with 5 ° of C min
-1Heating rate be heated to 260 ° of C and keep the heating 20h, make selenium fully be distributed in mesoporous carbon;
(3) stopped heating and fall back room temperature obtains selenium-mesoporous carbon complex.
(3) preparation selenium-mesoporous carrier complexes is anodal
With the selenium-mesoporous carbon complex of above-mentioned preparation with Super-P, binding agent sodium alginate (SA) with water mixes by a certain percentage, it is anodal namely to obtain selenium-mesoporous carbon complex through technological processes such as slurrying, smear, dryings.
(4) assembling lithium-selenium cell
The selenium of above-mentioned preparation-mesoporous carbon complex positive pole is assembled lithium-selenium cell with cathode of lithium, and electrolyte is selected carbonic ester electrolyte (the EC/DMC(volume ratio of 1M LiTFSI is 1:1) solution).
(5) lithium-selenium cell test
Use discharges and recharges instrument above-mentioned lithium-selenium cell is carried out constant current charge-discharge test, and the test voltage interval is 1.0-3.0V.Probe temperature is 25 ° of C, and battery capacity and charging and discharging currents are all with the Mass Calculation of simple substance selenium.Fig. 6 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 first circle discharge capacity of described lithium-selenium cell in above-mentioned voltage range is 862mA h g
-1, the first circle charging capacity is 602mA h g
-1, the second circle discharge capacity is 621mA h g
-1, be stabilized in gradually 550mA h g since the 3rd circle capacity
-1, cyclic curve is stable, coulombic efficiency approximately 100%, and discharge platform is single platform, is the 2V left and right.Fig. 7 is described lithium-selenium cell cycle performance under the 0.1C multiplying power in carbonic ester electrolyte.Described lithium-selenium cell is stabilized in 550mA h g since the 3rd circle capacity under the 0.1C multiplying power gradually in above-mentioned voltage range
-1, coulombic efficiency is near 100%, and through 20 circle circulations, capacity still remains on 525mA h g to described lithium-selenium cell under the 0.1C multiplying power
-1
Embodiment 4
(1) preparation mesoporous iron oxide carrier
The mesoporous carrier that adopts in experiment is mesoporous iron oxide, and specific area is 205m
2g
-1, pore volume is 0.262cm
3g
-1, average pore size is 7.1nm.
The preparation method of mesoporous iron oxide is as follows:
Press OH
-: Fe
3+The ratio of=2:1 is added drop-wise to FeCl with NaOH (0.1M)
3In (0.1M), after stirring 12h, under stirring condition, mixed liquor is added drop-wise in 80 ° of C oil baths in lauryl sodium sulfate (available from the Chemical Reagent Co., Ltd., Sinopharm Group) aqueous solution in solution, keeps 8h.Through 120 ° of C oven dry 5h after centrifuge washing, then in air 450 ° of C roasting 5h after 250 ° of C pre-burning 2h, namely obtain mesoporous iron oxide.
(2) preparation selenium-mesoporous carrier complexes
In prepared selenium in experiment-mesoporous iron oxide compound, the mass fraction of selenium is 33.3%.
The preparation method of selenium-mesoporous iron oxide compound is as follows:
(1) with selenium and mesoporous iron oxide in mass ratio the ratio of 0.5:1 weigh and evenly mix;
(2) mixture of selenium and mesoporous iron oxide is full of in the constant volume reactor of argon gas with 3 ° of C min
-1Heating rate be heated to 240 ° of C and keep the heating 24h, make selenium fully be distributed in mesoporous iron oxide;
(3) stopped heating and fall back room temperature obtains selenium-mesoporous iron oxide compound.
(3) preparation selenium-mesoporous carrier complexes is anodal
With above-mentioned preparation selenium-the mesoporous iron oxide compound is with Ketjen black, binding agent gelatin (available from Chemical Reagent Co., Ltd., Sinopharm Group) and water mixes by a certain percentage, it is anodal namely to obtain selenium-mesoporous iron oxide compound through technological processes such as slurrying, smear, dryings.
(4) assembling lithium-selenium cell
The selenium of above-mentioned preparation-mesoporous iron oxide compound positive pole is assembled lithium-selenium cell with cathode of lithium, and electrolyte is selected ester class electrolyte (1M LiClO
4The EC/PC/EMC(volume ratio be 1:1:1) solution).
(5) lithium-selenium cell test
Use discharges and recharges instrument above-mentioned lithium-selenium cell is carried out constant current charge-discharge test, and the test voltage interval is 1.0-3.0V.Probe temperature is 25 ° of C, and battery capacity and charging and discharging currents are all with the Mass Calculation of selenium.Described lithium-selenium cell first circle discharge capacity under the 0.1C multiplying power in above-mentioned voltage range is 1170mA hg
-1, the second circle beginning, capacity is stabilized in 650mA h g gradually
-1The left and right.Through 30 circle circulations, capacity still remains on 520mA h g to described lithium-selenium cell under the 0.1C multiplying power
-1Above.Has good capability retention.
In sum, lithium-selenium cell of the present invention is possessed high circulation volume, excellent room temperature cyclical stability and single discharge platform, the preparation method of its chief component selenium-mesoporous carrier complexes positive pole is simple, raw material is easy to get, suitable for mass production, thereby lithium-selenium cell of the present invention is expected to have a good application prospect as the alternative lithium ion battery that is widely adopted now of novel high volume energy density type energy storage device.
Foregoing is only the preferred embodiments of the present invention; will be appreciated that; this description is not for restriction embodiment of the present invention; those of ordinary skills are according to main design of the present invention and spirit; can carry out very easily corresponding flexible or modification, so protection scope of the present invention should be as the criterion with the desired protection range of claims.
Claims (10)
1. selenium-mesoporous carrier complexes, described compound is by selenium and the preparation of mesoporous carrier and get, and described selenium is dispersed in the mesopore orbit of described mesoporous carrier with the form of single ring-type selenium molecule and/or amorphous chain selenium molecule; The quality percentage composition of described selenium in described mesoporous carrier is 10-90%.
2. compound according to claim 1, it is characterized in that: described mesoporous carrier is selected from one or more in the mesoporous carrier of carbon and the mesoporous carrier of non-carbon;
The specific surface of described mesoporous carrier is 200-3000m
2g
-1, pore volume is 0.2-10cm
3g
-1, average pore size is 2-50nm, preferably, described pore volume is 0.5-5.0cm
3g
-1, more preferably, described pore volume is 0.8-3.0cm
3g
-1Also preferably, described average pore size is 2-10nm, more preferably 2-5nm.
Preferably, the mesoporous carrier of described non-carbon specifically is selected from one or more in mesoporous metal, mesopore metal oxide, mesoporous semiconductive ceramic, mesopore molecular sieve and mesoporous phosphate material;
Wherein, described mesoporous metal is selected from one or more in mesoporous gold, mesoporous platinum, mesoporous aluminium, mesoporous nickel and mesoporous titanium;
Described mesopore metal oxide is selected from one or more in mesoporous di-iron trioxide, mesoporous ferriferrous oxide, mesoporous TiO 2 and mesoporous ruthenium-oxide;
Described mesoporous semiconductive ceramic is selected from one or more in mesoporous silicon carbide and mesoporous zinc oxide;
Described mesopore molecular sieve is selected from one or more in MCM series and SBA series mesopore molecular sieve.
Described mesoporous phosphate material is selected from one or more in mesoporous aluminum phosphate, mesoporous titanium phosphate, mesoporous vanadium phosphate, mesoporous ferric phosphate, mesoporous trbasic zinc phosphate.
3. method for preparing the arbitrary described selenium of claim 1-2-mesoporous carrier complexes, comprise the steps: and to be warming up to 220-300 ° of C insulation at the constant volume reactor that is full of one or more inert gas atmospheres such as nitrogen, argon gas after selenium and described mesoporous carrier mixing, stopped heating is cooled to room temperature again, obtains described selenium-mesoporous carrier complexes.Preferably, the mass ratio of described selenium and described mesoporous carrier is 0.1:1～9:1, more preferably 0.25:1～4:1.
4. selenium-mesoporous carrier composite positive pole, it comprises the described compound of claim 1-2 any one.
5. preparation method who prepares the described selenium of claim 4-mesoporous carrier composite positive pole, comprise the steps: and to be warming up to 220-300 ° of C insulation at the constant volume reactor that is full of one or more inert gas atmospheres such as nitrogen, argon gas after selenium and described mesoporous carrier mixing, stopped heating is cooled to room temperature again, obtains described selenium-mesoporous carrier complexes.
6. method according to claim 5, it is characterized in that: the mass ratio of described selenium and described mesoporous carrier is 0.1:1～9:1, preferred 0.25:1～4:1 also is preferably 1:1～3:1.
7. selenium-mesoporous carrier complexes electrode and preparation method thereof, it is characterized in that described material contains the arbitrary described selenium of claim 1-2-mesoporous carrier complexes or selenium claimed in claim 4-mesoporous carrier composite positive pole, and contain conductive additive, binding agent and coordinative solvent.If protection preparation method, the method comprise described selenium-mesoporous carrier complexes positive electrode, make through slurrying, smear, dry technological process.
8. selenium according to claim 7-mesoporous carrier complexes electrode, it is characterized in that: preferably, described conductive additive is one or more in carbon black, Super-P, Ketjen black;
Preferably, described binding agent and coordinative solvent are one or more in Kynoar (PVDF) (take 1-METHYLPYRROLIDONE (NMP) as 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 uses with the form of the aqueous solution.
9. a lithium-selenium cell, comprise lithium metal, anodal claim 7 or the described selenium of 8 any one-mesoporous carrier complexes electrode and the organic electrolyte of conduct as negative pole.Preferably, described organic electrolyte is carbonic ester electrolyte or ether electrolyte, and concentration is 0.1-2M, preferred 0.5-1.5M;
In described carbonic ester electrolyte, solvent is selected from one or more 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) and two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI) in one or more;
In described ether electrolyte, solvent is selected from one or more in DOX (DOL), glycol dimethyl ether (DME) and TRIGLYME (TEGDME), and solute is selected from lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4) and two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI) in one or more.
10. the application of the described lithium-selenium cell of claim 9 in the high volume energy density type energy storage device of preparation.
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| CN104201349A (en) * | 2014-08-13 | 2014-12-10 | 东南大学 | Preparation method of selenium-carbon electrode material with porous structure and application of selenium-carbon electrode material |
| CN104393304A (en) * | 2014-11-13 | 2015-03-04 | 清华大学深圳研究生院 | Lithium-selenium battery positive electrode material, preparation method thereof and lithium-selenium battery |
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| CN104638230A (en) * | 2015-01-30 | 2015-05-20 | 浙江工业大学 | Method for preparing selenium-carbon composite material from supercritical carbon dioxide |
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| CN104393304A (en) * | 2014-11-13 | 2015-03-04 | 清华大学深圳研究生院 | Lithium-selenium battery positive electrode material, preparation method thereof and lithium-selenium battery |
| CN104600296A (en) * | 2014-12-31 | 2015-05-06 | 山东玉皇新能源科技有限公司 | Preparation method of Se-C positive electrode composite material of lithium-selenium battery |
| CN104638230A (en) * | 2015-01-30 | 2015-05-20 | 浙江工业大学 | Method for preparing selenium-carbon composite material from supercritical carbon dioxide |
| CN105161687A (en) * | 2015-09-16 | 2015-12-16 | 中国计量学院 | Preparation method of selenium composite electrode material |
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| US11515518B2 (en) | 2015-09-22 | 2022-11-29 | Institute Of Chemistry, Chinese Academy Of Sciences | Immobilized selenium, a method of making, and uses of immobilized selenium in a rechargeable battery |
| CN105070892B (en) * | 2015-09-22 | 2018-03-06 | 中国科学院化学研究所 | A kind of preparation method and application of selenium carbon complex |
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| US11843109B2 (en) | 2015-09-22 | 2023-12-12 | Ii-Vi Delaware, Inc. | Method of preparing and application of carbon-selenium composites |
| US11784303B2 (en) | 2015-09-22 | 2023-10-10 | Ii-Vi Delaware, Inc. | Immobilized chalcogen and use thereof in a rechargeable battery |
| EP3353841A4 (en) * | 2015-09-22 | 2019-06-05 | Institute of Chemistry, Chinese Academy of Science | Method of preparing and application of carbon-selenium composites |
| CN105070892A (en) * | 2015-09-22 | 2015-11-18 | 中国科学院化学研究所 | Preparation method and application of selenium-carbon compound |
| 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 |
| 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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| US11482698B2 (en) | 2015-09-22 | 2022-10-25 | Ii-Vi Delaware, Inc. | Immobilized selenium, a method of making, and uses of immobilized selenium in a rechargeable 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 |
| CN106784660A (en) * | 2016-12-02 | 2017-05-31 | 吉林大学 | Nickel foam as interlayer Se TiO2/ NFF lithium selenium secondary cells and preparation method thereof |
| CN109565029B (en) * | 2017-02-07 | 2021-11-26 | 株式会社Lg化学 | Method for manufacturing long-life electrode of secondary battery |
| CN109565029A (en) * | 2017-02-07 | 2019-04-02 | 株式会社Lg化学 | The method for manufacturing the electrode of the long-life of secondary cell |
| 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 |
| US20190326587A1 (en) * | 2018-04-18 | 2019-10-24 | Nanotek Instruments, Inc. | Selenium Loaded Mesoporous Carbon Cathode for Alkali Metal-Selenium Secondary Battery |
| CN115441123B (en) * | 2022-10-14 | 2024-03-08 | 贺州学院 | High-liquid-absorption and high-flame-retardance battery diaphragm and preparation method thereof |
| CN115441123A (en) * | 2022-10-14 | 2022-12-06 | 贺州学院 | High-liquid-absorption-rate and high-flame-retardance battery diaphragm and preparation method thereof |
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