CN103872293A - Novel lithium ion battery electrode material and application of lithium ion battery electrode material - Google Patents
Novel lithium ion battery electrode material and application of lithium ion battery electrode material Download PDFInfo
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- CN103872293A CN103872293A CN201410101204.4A CN201410101204A CN103872293A CN 103872293 A CN103872293 A CN 103872293A CN 201410101204 A CN201410101204 A CN 201410101204A CN 103872293 A CN103872293 A CN 103872293A
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
The invention discloses a novel tellurium-based electrode and application of the novel tellurium-based electrode in a lithium-tellurium battery and a lithium ion battery. An electrode material is selected from a tellurium-carrier material composite. The lithium ion battery comprises a positive electrode, a negative electrode and electrolyte; an active substance of the negative electrode is selected from a tellurium-based material. The lithium ion battery provided by the invention has the characteristics of high safety, high specific capacity and stable circulation.
Description
Technical field
The preparation and the field of electrochemical power source that the invention belongs to energy and material, be specifically related to a kind of lithium ion battery electrode material.
Background technology
Lithium ion battery is the new generation of green environment-friendly battery of putting on market after the nineties, it because high, the specific energy of operating voltage large, have extended cycle life, self discharge power is little, memory-less effect, the advantage such as pollution-free and be widely used in portable electronics and electric automobile.In recent years, especially the demand of portable set is gradually increased, exploitation small size, large capacity, long-life, high efficiency lithium-ion battery system are the focuses of studying at present.Tellurium, a kind of semi-conducting material with high electrical conductivity, as photoelectric conversion material for energy conversion device (as, CN102360962A) or as catalyst material in fuel cell (as, CN102593472A).But be not also used in lithium ion battery electrode material.
Summary of the invention
The invention provides a kind of telluro material, it comprises tellurium-carrier material compound, and described tellurium-carrier material compound is selected from one or more in tellurium/carbon complex, tellurium/metal oxide compounds, tellurium/sulfur family metallic compound, tellurium/conductive polymer composite;
Wherein, described metal oxide is selected from one or more in manganese oxide, titanium oxide, cobalt oxide, tin oxide, tungsten oxide;
Described tellurium/carbon complex comprises: tellurium/porous carbon compound, tellurium/carbon mano-tube composite, tellurium/graphene complex, tellurium/carbon black compound, tellurium/graphite composite, tellurium/carbonaceous mesophase spherules compound; Porous carbon is selected from the material with carbon element that contains in macropore, mesoporous, micropore and graded porous carbon at least one; Carbon black is selected from one or more in acetylene black, Ketjen black; Graphite is selected from one or more in native graphite, electrographite, modified graphite;
Described conducting polymer is selected from one or more of polypyrrole, polyaniline, polyacetylene, polythiophene, polyphenyl, polyacrylonitrile.
Described sulfur family metallic compound comprises metal sulfide, metal selenide, metal telluride.Wherein metal is at least selected from one or more in Ca, Ti, Fe, Ni, Cu, Zn, Nb, Pb, Sb, Ge.
Preferably, described tellurium-carrier material compound is selected from tellurium/carbon composite and tellurium/sulfur family metallic compound.Especially preferred, described tellurium-carrier material compound is selected from tellurium/microporous carbon carrier complexes, tellurium/tellurium carbon/carbon-copper composite material, tellurium/polypyrrole/tellurium carbon/carbon-copper composite material.The invention provides a kind of telluro electrode material.This electrode contains above-mentioned telluro material, binding agent and conductive additive.
Further, binding agent is the combination of water system binding agent or water system binding agent and organic system binding agent; Water system binding agent is selected from: sodium alginate, sodium carboxymethylcellulose, sodium carboxymethylcellulose and butadiene-styrene rubber compound, cyclodextrin, one or more in poly(ethylene oxide); Organic system binding agent is selected from: Kynoar, polytetrafluoroethylene, one or more in polyvinylpyrrolidone.Preferably, effect optimum when described binding agent is sodium carboxymethylcellulose and butadiene-styrene rubber compound.
Further, conductive additive is selected from the one of Super-P(conductive black), Ketjen black (ketjenblack EC-600JD, the one of conductive black), carbon nano-tube, one or more mixtures in Graphene.Preferably, described conductive additive is Graphene, Ketjen black and Super-P effect optimum during with 1:0.5:0.5.
The invention provides a kind of lithium metal secondary battery, comprise as the lithium metal of negative pole, as anodal above-mentioned telluro electrode material and organic electrolyte.
Further, electrolyte is selected from liquid electrolyte and solid electrolyte;
Wherein, described liquid electrolyte comprises the electrolyte based on protic organic solvent and ionic liquid; Solid electrolyte comprises inorganic solid electrolyte, gel polymer electrolyte and solid polymer electrolyte;
Electrolyte based on protic organic solvent is selected from ether electrolyte and carbonic ester electrolyte; The solvent of ether electrolyte is selected from least one in DOX, glycol dimethyl ether and TRIGLYME, and solute is selected from least one in lithium hexafluoro phosphate, lithium perchlorate, lithium iodide and two (trimethyl fluoride sulfonyl) imine lithium; The solvent of carbonic ester electrolyte 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 lithium hexafluoro phosphate, sodium perchlorate, lithium iodide and two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI);
Described inorganic solid electrolyte is selected from one or more solid-state ceramic electrolyte;
Described polymer dielectric is selected from one or more in the copolymer (PVDF-HFP) of poly(ethylene oxide) (PEO), Polyethylene glycol dimethyl ether (PEGDME), vinylidene fluoride and hexafluoropropylene.
The invention provides a kind of lithium ion battery, comprise can reversible doff lithium positive pole, negative pole and electrolyte, it is characterized in that, negative pole is using telluro material as active material, and in described positive pole and negative pole, all comprises binding agent, preferably, in described negative or positive electrode, comprise water-soluble glue as binding agent, particularly preferably, in described positive pole and negative pole, all comprise water-soluble glue as binding agent.
Further, positive electrode is lithium intercalation compound, be selected from lithium transition-metal oxide and polyanion positive electrode, be selected from LiMn2O4 and compound thereof, tertiary cathode material (LiNixCoyMn1-x-yO2) and compound thereof, cobalt acid lithium and compound thereof, LiFePO4 and compound thereof, rich lithium material and compound thereof (xLi2MnO3 (1-x) LiMO2 (M=Co, Ni, Mn)).
Further, binding agent is the combination of water system binding agent or water system binding agent and organic system binding agent; Water system binding agent is selected from: sodium alginate, sodium carboxymethylcellulose, sodium carboxymethylcellulose and butadiene-styrene rubber compound, cyclodextrin, one or more in poly(ethylene oxide); Organic system binding agent is selected from: Kynoar, polytetrafluoroethylene, one or more in polyvinylpyrrolidone.
Preferably, described binding agent is sodium carboxymethylcellulose and butadiene-styrene rubber compound.
Further, conductive additive is selected from carbon black, Ketjen black, carbon nano-tube, Graphene, one or more in Super-P.Preferably, described conductive additive is the mixture of Graphene, Ketjen black and Super-P carbon black, preferred, for Graphene, Ketjen black and Super-P are with the mixture of the ratio formation of 1:0.2-0.6:0.2-0.6.
Further, electrolyte is selected from liquid electrolyte and solid electrolyte;
Wherein, described liquid electrolyte comprises the electrolyte based on protic organic solvent and ionic liquid; Solid electrolyte comprises inorganic solid electrolyte, gel polymer electrolyte and solid polymer electrolyte;
Electrolyte based on protic organic solvent is selected from ether electrolyte and carbonic ester electrolyte; The solvent of ether electrolyte is selected from least one in DOX, glycol dimethyl ether and TRIGLYME, and solute is selected from least one in lithium hexafluoro phosphate, lithium perchlorate, lithium iodide and two (trimethyl fluoride sulfonyl) imine lithium; The solvent of carbonic ester electrolyte 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 lithium hexafluoro phosphate, sodium perchlorate, lithium iodide and two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI);
Described inorganic solid electrolyte is selected from one or more solid-state ceramic electrolyte;
Described polymer dielectric is selected from one or more in the copolymer (PVDF-HFP) of poly(ethylene oxide) (PEO), Polyethylene glycol dimethyl ether (PEGDME), vinylidene fluoride and hexafluoropropylene.
Further, adhesive is sodium carboxymethylcellulose and butadiene-styrene rubber compound, just very ternary material, and while adopting electrolyte for [the EC/DMC/DEC(volume ratio of 1M LiPF6 is 1:1:1) solution], effect is best.
The present invention also provides a kind of energy storage elements, and described energy storage elements contains described telluro material, this energy storage elements preferred lithium ion battery.
Brief description of the drawings
Fig. 1 is the constant current charge-discharge curve of the lithium tellurium battery of embodiment 1.
Fig. 2 is the cycle performance of lithium tellurium battery in embodiment 1.
Fig. 3 is the lithium ion battery of embodiment 1 charge-discharge performance under 0.1C.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Experimental technique described in following embodiment, if no special instructions, is conventional method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Assembling and the electrochemical property test of embodiment 1, tellurium/microporous carbon combination electrode and lithium tellurium battery thereof, lithium ion battery.
1-1 prepares tellurium/microporous carbon carrier composite material
By after simple substance tellurium and micro-pore carbon material mixing and ball milling 12h, under argon gas atmosphere, 600 DEG C keep 15h, 400 DEG C of maintenance 6h of rear continuation.Stop again heating and be cooled to room temperature, obtain tellurium/microporous carbon carrier composite material.
1-2 prepares tellurium/microporous carbon carrier combination electrode
Electrode comprises the active material of above-mentioned preparation, conductive additive, binding agent.Wherein, conductive additive is the mixture that Graphene, Ketjen black, Super P are 1:0.5:0.5 according to mass ratio.By tellurium/microporous carbon compound and Graphene, sodium carboxymethylcellulose and butadiene-styrene rubber compound in mass ratio 7:2:1 mix, obtain tellurium/microporous carbon carrier complexes electrode through slurrying, smear, the technological process such as dry.
1-3 assembling lithium tellurium battery and test thereof
Tellurium/microporous carbon carrier complexes of above-mentioned preparation is assembled to lithium tellurium battery with lithium, electrolyte selection carbonic ester electrolyte [the EC/DMC(volume ratio of 1M LiPF6 is 1:1 solution)].Use discharges and recharges instrument above-mentioned lithium tellurium battery is carried out to constant current charge-discharge test, and test voltage interval is 1-3V, and probe temperature is 25 DEG C.Battery capacity and charging and discharging currents are all with the Mass Calculation of tellurium-carbon complex.Fig. 1 is that in described lithium tellurium battery, 0.1C(is equivalent to 42mA g-1) constant current charge-discharge curve under multiplying power.Described lithium tellurium electrode first circle discharge capacity is 570mA h/g, and first circle charging capacity is 400mA h/g, and the second circle discharge capacity still has 430mA h/g.Fig. 2 is the cycle performance of described lithium tellurium battery under 0.1C multiplying power.Described lithium tellurium battery circulates through 50 circles, and discharge capacity still remains on 400mA h/g, has good capability retention and coulomb efficiency.
1-4 assembles lithium ion battery
The preparation of 1-4-1 positive pole
In tertiary cathode material (LiCo0.3Ni0.3Mn0.3O2): conductive carbon black (Graphene, Ketjen black and Super-P are with the mixture of 1:0.5:0.5): the ratio (mass ratio) of sodium carboxymethylcellulose and butadiene-styrene rubber compound=8:1:1 is mixed, after mixing, be coated on collector, after vacuumize, section, obtain tertiary cathode.
The assembling of 1-4-2 lithium ion battery
Taking above-mentioned tellurium/microporous carbon carrier material as negative pole, above-mentioned tertiary cathode material is anodal, between positive pole and negative pole, insert glass fibre membrane (Whatman company of Britain) as barrier film, add carbonic ester electrolyte [the EC/DMC/DEC(volume ratio of 1M LiPF6 is 1:1:1) solution].
The test of 1-4-3 lithium ion battery
The lithium ion battery of above-mentioned assembling is carried out on charge-discharge test instrument to charge-discharge test, the interval that discharges and recharges of test is 1.0 3.2V.Probe temperature is 25 DEG C, and battery capacity and the charging and discharging currents all quality based on positive electrode calculate.Fig. 1 is the charging and discharging curve of the described lithium ion battery based on tertiary cathode/tellurium carbon negative pole under 0.1C condition, and under 0.1C condition, specific discharge capacity reaches 150mAh/g.And capability retention is still 120mA h/g after 50 circle circulations.
Comparative example 1-1
Other conditions are identical with embodiment 1, and difference is only that active material is simple substance tellurium but not composite material in embodiment 1.By the electrode making and lithium metal composition lithium tellurium battery testing, first circle discharge capacity is 250mA h g-1, and after 40 circle circulations, capacity only can remain on 50mA h g-1.This tellurium electrode is assembled into lithium ion battery as negative pole and tertiary cathode material, and the first circle discharge capacity recording is 80mA h g-1, and after 50 circle circulations, capacity only can remain on 40mA h g-1.
Embodiment 2, other condition are identical with embodiment 1, the conductive additive that difference is only to prepare tellurium/microporous carbon carrier combination electrode is carbon nano-tube, by the electrode making and lithium metal composition lithium tellurium battery testing, first circle discharge capacity is 600mA h g-1, after 50 circle circulations, capacity only can remain on 370mA h g-1.This tellurium/microporous carbon carrier combination electrode is assembled into lithium ion battery as negative pole and tertiary cathode material, and the first circle discharge capacity recording is 135mA h g-1, and after 50 circle circulations, capacity can remain on 115mA h g-1.
The assembling of embodiment 3, tellurium/mesoporous carbon composite electrode and lithium ion battery thereof and electrochemical property test.
Other condition is identical with embodiment 1, and difference is only that carbon substrate is mesoporous carbon CMK-3, and by the electrode making and lithium metal composition lithium tellurium battery testing, first circle discharge capacity is 450mA h g-1, and after 50 circle circulations, capacity can remain on 250mA h g-1.This tellurium/microporous carbon carrier combination electrode is assembled into lithium ion battery as negative pole and tertiary cathode material, and the first circle discharge capacity recording is 110mA h g-1, and after 50 circle circulations, capacity can remain on 80mA h g-1.
Assembling and the electrochemical property test of embodiment 4, tellurium/Jie microporous carbon combination electrode and lithium ion battery thereof.
Other condition is identical with embodiment 1, and difference is only that carbon substrate is Jie's micropore composite carbon, and by the electrode making and lithium metal composition lithium tellurium battery testing, first circle discharge capacity is 530mA h g-1, and after 50 circle circulations, capacity can remain on 300mA h g-1.This tellurium/microporous carbon carrier combination electrode is assembled into lithium ion battery as negative pole and tertiary cathode material, and the first circle discharge capacity recording is 120mA h g-1, and after 50 circle circulations, capacity can remain on 95mA h g-1.
Assembling and the electrochemical property test of embodiment 5, tellurium/tin oxide combination electrode and lithium ion battery thereof.
5-1 prepares tellurium/tin oxide composite material
By after simple substance tellurium and tin oxide mixing and ball milling 12h, under argon gas atmosphere, 600 DEG C keep 15h, 400 DEG C of maintenance 6h of rear continuation.Stop again heating and be cooled to room temperature, obtain described tellurium/tin oxide composite material.
5-2 prepares tellurium-tin oxide combination electrode
Electrode comprises the active material of above-mentioned preparation, conductive additive, binding agent.Wherein, conductive additive is the mixture that Graphene, Ketjen black, Super P are 1:0.5:0.5 according to mass ratio.By tellurium/porous oxidation tin and Graphene, sodium carboxymethylcellulose and butadiene-styrene rubber compound in mass ratio 8:1:1 mix, obtain tellurium/tin oxide combination electrode through slurrying, smear, the technological process such as dry.
5-3 assembling lithium tellurium battery and test thereof
Tellurium/tin oxide combination electrode of above-mentioned preparation is assembled to lithium-tellurium battery with lithium.Electrolyte selection carbonic ester electrolyte [the EC/DMC(volume ratio of 1M LiPF6 is 1:1 solution)].Use discharges and recharges instrument above-mentioned lithium tellurium battery is carried out to constant current charge-discharge test, and test voltage interval is 1.0-2.7V, and probe temperature is 25 DEG C.Described lithium tellurium electrode first circle discharge capacity is 400mA h/g.Described lithium tellurium battery circulates through 40 circles, and discharge capacity still remains on 335mA h/g and has good capability retention and coulomb efficiency.
5-4 assembles lithium ion battery
The preparation of 5-4-1 positive pole
In tertiary cathode material (LiCo0.3Ni0.3Mn0.3O2): conductive carbon black (Graphene, Ketjen black and Super-P are with the mixture of 1:0.5:0.5): the ratio (mass ratio) of sodium carboxymethylcellulose and butadiene-styrene rubber compound=8:1:1 is mixed, after mixing, be coated on collector, after vacuumize, section, obtain tertiary cathode.
The assembling of 5-4-2 lithium ion battery
Taking above-mentioned tellurium carbon electrode as negative pole, ternary material is anodal, inserts glass fibre membrane (Whatman company of Britain) as barrier film between positive pole and negative pole, adds carbonic ester electrolyte [the EC/DMC/DEC(mass ratio of 1M LiPF6 is 1:1) solution].
The test of 5-4-3 lithium ion battery
The lithium ion battery of above-mentioned assembling is carried out on charge-discharge test instrument to charge-discharge test, the interval that discharges and recharges of test is 1.0 3.2V.Probe temperature is 25 DEG C, and battery capacity and the charging and discharging currents all quality based on positive electrode calculate.Under 0.1C condition, specific discharge capacity reaches 105mA h/g.And capability retention is still 80mA h/g after 50 circle circulations.
Assembling and the electrochemical property test of embodiment 6, tellurium/tellurium copper combination electrode and lithium tellurium battery/lithium ion battery thereof.
6-1 prepares tellurium/tellurium carbon/carbon-copper composite material
Weigh Na2TeO30.23g, add 5mL H2O and dissolve, stir 5min.Add 15mL acetone (CH3COCH3), stir 5min, then dropwise add 5mL diamine.Stir 10min, add 0.5g Schweinfurt green Cu (Ac) 2, stir 15min, after adding the mesoporous SiO2 of 200mg (SBA-15), pack 50mL reactor into, be full of kettle long-pending 80%. will after still sealing, put into baking oven, react 16h. after still takes out at 180 DEG C, allow it naturally cool to room temperature, successively use deionized water and absolute ethanol washing sample repeatedly, put into the dry 6h of vacuum drying chamber.With 10%HF solution soak 10h, repeatedly wash to pH be 7.0, vacuumize 6h, obtains tellurium copper carrier material.By after simple substance tellurium and the tellurium copper carrier mixing and ball milling 12h that makes, under argon gas atmosphere, 400 DEG C keep 10h.Stop again heating and be cooled to room temperature, obtain described tellurium/tellurium carbon/carbon-copper composite material.
6-2 prepares tellurium/tellurium copper combination electrode
Mixture, sodium carboxymethylcellulose and the butadiene-styrene rubber complex binder that is 1:0.5:0.5 with Graphene, Ketjen black, Super P according to mass ratio by tellurium/tellurium copper composition of above-mentioned preparation in mass ratio 8:1:1 mixes, through slurrying, smear, the technological process such as dry, obtain tellurium/tellurium copper composition electrode.
6-3 assembling lithium tellurium battery and test thereof
Tellurium/tellurium copper composition of above-mentioned preparation is selected to carbonic ester electrolyte [the EC/DMC(volume ratio of 1M LiPF6 is 1:1 solution)] with lithium assembling lithium tellurium battery electrolyte.Use discharges and recharges instrument above-mentioned lithium tellurium battery is carried out to constant current charge-discharge test, and test voltage interval is 1.0-3.0V, and probe temperature is 25 DEG C.Battery capacity and charging and discharging currents are all with the Mass Calculation of tellurium/tellurium copper composition.The first circle discharge capacity of described lithium tellurium battery in above-mentioned voltage range is 610mA h/g, and through 50 circle circulations, capacity still remains on 420mA h/g, has good capability retention and coulomb efficiency.
6-4 assembles lithium ion battery
The preparation of 6-4-1 positive pole
Tertiary cathode material: conductive carbon black (Graphene, Ketjen black and Super-P are with the mixture of 1:0.5:0.5): the ratio (mass ratio) of sodium carboxymethylcellulose and butadiene-styrene rubber compound=8:1:1 is mixed, after mixing, be coated on collector, after vacuumize, section, obtain tertiary cathode.
The assembling of 6-4-2 lithium ion battery
Taking above-mentioned tellurium/tellurium copper combination electrode as negative pole, ternary material is positive electrode, between positive pole and negative pole, insert glass fibre membrane (Whatman company of Britain) as barrier film, add carbonic ester electrolyte [the EC/DMC/DEC(volume ratio of 1M LiPF6 is 1:1:1) solution].
The test of 6-4-3 lithium ion battery
The lithium ion battery of above-mentioned assembling is carried out on charge-discharge test instrument to charge-discharge test, the interval that discharges and recharges of test is 1.0 3.2V.Probe temperature is 25 DEG C, and battery capacity and the charging and discharging currents all quality based on positive electrode calculate.Under 0.1C condition, specific discharge capacity reaches 123mA h/g.And capacity can remain on 105mA h/g after 50 circle circulations.
Embodiment 7, other condition are identical with embodiment 6, difference is only that carrier material is copper selenide Cu2Se, and by the electrode making and lithium metal composition lithium tellurium battery testing, first circle discharge capacity is 450mA h g-1, after 50 circle circulations, capacity can remain on 380mA h g-1.This tellurium/Cu2Se combination electrode is assembled into lithium ion battery as negative pole and tertiary cathode material, and the first circle discharge capacity recording is 115mA h g-1, and after 50 circle circulations, capacity can remain on 103mA h g-1.
Embodiment 8, other condition are identical with embodiment 6, difference is only that carrier material is copper sulfide Cu2S, and by the electrode making and lithium metal composition lithium tellurium battery testing, first circle discharge capacity is 400mA h g-1, after 50 circle circulations, capacity only can remain on 320mA h g-1.This tellurium/microporous carbon carrier combination electrode is assembled into lithium ion battery as negative pole and tertiary cathode material, and the first circle discharge capacity recording is 105mA h g-1, and after 50 circle circulations, capacity can remain on 86mA h g-1.
Assembling and the electrochemical property test of embodiment 9, tellurium/polypyrrole combination electrode and lithium tellurium battery/lithium ion battery thereof
9-1 prepares tellurium/polypyrrole combination electrode material
By simple substance tellurium with 800r/min speed ball milling 12h after, be placed in the ultrasonic 1h of polypyrrole dispersion liquid, the two mass ratio is 4:1.
9-2 prepares tellurium/polypyrrole combination electrode
Mixture, sodium carboxymethylcellulose and the butadiene-styrene rubber complex binder that is 1:0.5:0.5 with Graphene, Ketjen black, Super P according to mass ratio by the tellurium/Pt/Polypyrrole composite material of above-mentioned preparation in mass ratio 8:0.5:0.5:1 mixes, and obtains tellurium/polypyrrole composite electrode through slurrying, smear, the technological process such as dry.
9-3 assembling lithium tellurium battery and test
By the lithium tellurium electrode of above-mentioned preparation, with lithium assembling lithium tellurium battery, electrolyte is selected carbonic ester electrolyte (the EC/DMC(mass ratio of 1M LiPF6 is 1:1 solution)).Use discharges and recharges instrument above-mentioned lithium tellurium battery is carried out to constant current charge-discharge test, and test voltage interval is 1.0-3.0V, and probe temperature is 25 DEG C.Battery capacity and charging and discharging currents are all with the Mass Calculation of simple substance tellurium.Described battery is under 0.1C condition, and first circle discharge capacity is 382mA h/g, and through 50 circle circulations, capacity still remains on 305mAh/g.
9-4 assembles lithium ion battery
The preparation of 9-4-1 positive pole
Conductive carbon black (Graphene, Ketjen black and Super-P are with the mixture of 1:0.5:0.5): the ratio (mass ratio) of sodium carboxymethylcellulose and butadiene-styrene rubber compound=8:1:1 is mixed, after mixing, be coated on collector, after vacuumize, section, obtain ternary material positive pole.
The assembling of 9-4-2 lithium ion battery
Taking above-mentioned tellurium/polypyrrole combination electrode as negative pole, ternary material is positive electrode, between positive pole and negative pole, insert glass fibre membrane (Whatman company of Britain) as barrier film, add carbonic ester electrolyte [the EC/DMC/DEC(volume ratio of 1M LiPF6 is 1:1:1) solution].
The test of 9-4-3 lithium ion battery
The lithium ion battery of above-mentioned assembling is carried out on charge-discharge test instrument to charge-discharge test, the interval that discharges and recharges of test is 1.0 3.2V.Probe temperature is 25 DEG C, and battery capacity and the charging and discharging currents all quality based on positive electrode calculate.Under 0.1C condition, first circle specific discharge capacity reaches 107mAh/g.And capacity still can remain on 87mA h/g after 50 circle circulations.
Assembling and the electrochemical property test of embodiment 10 telluriums/polypyrrole/tellurium copper combination electrode and lithium tellurium battery/lithium ion battery thereof
10-1 prepares tellurium/polypyrrole/tellurium carbon/carbon-copper composite material
By simple substance tellurium in mass ratio 1:1 mix with tellurium copper, after 800r/min speed ball milling 12h, be placed in the ultrasonic 1h of polypyrrole dispersion liquid, obtain tellurium/polypyrrole/tellurium carbon/carbon-copper composite material.
10-2 prepares tellurium/polypyrrole/tellurium copper combination electrode
Mixture, sodium carboxymethylcellulose and the butadiene-styrene rubber binding agent that is 1:0.5:0.5 with Graphene, Ketjen black, Super P according to mass ratio by the tellurium/polypyrrole of above-mentioned preparation/tellurium carbon/carbon-copper composite material in mass ratio 8:0.5:0.5:1 mixes, and obtains tellurium/polypyrrole/tellurium copper combination electrode through slurrying, smear, the technological process such as dry.
10-3 assembling lithium tellurium battery and test
Tellurium/the polypyrrole of above-mentioned preparation/tellurium copper combination electrode is assembled to lithium tellurium battery with lithium, electrolyte selection carbonic ester electrolyte [the EC/DMC(mass ratio of 1M LiPF6 is 1:1 solution)].Use discharges and recharges instrument above-mentioned lithium tellurium battery is carried out to constant current charge-discharge test, and test voltage interval is 1.0-3.0V, and probe temperature is 25 DEG C.Battery capacity and charging and discharging currents be the Mass Calculation based on tellurium/polypyrrole/tellurium copper composition all.Described battery is tested under 0.1C condition, and first circle discharge capacity is 620mA h/g, and through 50 circle circulations, capacity still remains on 460mA h/g.
10-4 assembles lithium ion battery
The preparation of 10-4-1 positive pole
Conductive carbon black (Graphene, Ketjen black and Super-P are with the mixture of 1:0.5:0.5): the ratio (mass ratio) of sodium carboxymethylcellulose and butadiene-styrene rubber compound=8:1:1 is mixed, after mixing, be coated on collector, after vacuumize, section, obtain tertiary cathode.
The assembling of 10-4-2 lithium ion battery
Taking above-mentioned tellurium/polypyrrole/tellurium copper combination electrode as negative pole, ternary material is anodal, between positive pole and negative pole, insert glass fibre membrane (Whatman company of Britain) as barrier film, add carbonic ester electrolyte [the EC/DMC/DEC(volume ratio of 1M LiPF6 is 1:1:1) solution].
The test of 10-4-3 lithium ion battery
The lithium ion battery of above-mentioned assembling is carried out on charge-discharge test instrument to charge-discharge test, the interval that discharges and recharges of test is 1.0 3.2V.Probe temperature is 25 DEG C, and battery capacity and the charging and discharging currents all quality based on positive electrode calculate.Under 0.1C condition, specific discharge capacity reaches 155mA h/g.And Capacitance reserve is at 120mA h/g after 50 circle circulations.
In sum, telluro electrode material provided by the invention has higher specific capacity and excellent cyclical stability, thereby lithium tellurium battery of the present invention and the lithium ion battery using telluro electrode as negative pole be expected to energy storage device good as a kind of novel fail safe and that energy density is high, have 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 main design of the present invention and spirit; can carry out very easily corresponding flexible or amendment, therefore protection scope of the present invention should be as the criterion with the desired protection range of claims.
Claims (9)
1. a telluro material, comprises tellurium-carrier material compound, and described carrier material is selected from metal oxide, carbon, conducting polymer, sulfur family metallic compound;
Wherein, described metal oxide is selected from one or more in manganese oxide, titanium oxide, cobalt oxide, tin oxide, tungsten oxide;
Described carbon carrier comprises: porous carbon, carbon nano-tube, Graphene; Porous carbon is selected from the material with carbon element that contains in macropore, mesoporous, micropore and graded porous carbon at least one; Carbon black is selected from one or more in acetylene black, Ketjen black and Super-P;
Described conducting polymer is selected from one or more of polypyrrole, polyaniline, polyacetylene, polythiophene, polyphenyl, polyacrylonitrile;
Described sulfur family metallic compound comprises metal sulfide, metal selenide, metal telluride, and the metal in wherein said sulfur family metallic compound is at least selected from one or more in Li, Na, K, Mg, Ca, Sr, Ba, Al, Ga, Sn, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Nb, Ag, W, Pb, Sb, Ge, Mo.
2. a preparation method for telluro material, is characterised in that: by after simple substance tellurium and carrier material mixing and ball milling 12h, under argon gas atmosphere, 600 DEG C keep 15h, take out rear 400 DEG C keep 6h, then stop heating being cooled to room temperature, obtain described telluro composite material.
3. a telluro Material cladding electrode, is characterized in that described material contains tellurium-carrier material compound claimed in claim 1, and contains conductive additive, binding agent and coordinative solvent,
Described conductive additive is Super-P,, Ketjen black,, one or more in Graphene, carbon nano-tube, preferably, described conductive additive is the mixture that Graphene, Ketjen black, Super-P carbon black form by the mol ratio of 1:0.2～0.6:0.2～0.6.
Described binding agent is the combination of water system binding agent or water system binding agent and organic system binding agent; Water system binding agent is selected from: sodium alginate, sodium carboxymethylcellulose, sodium carboxymethylcellulose and butadiene-styrene rubber compound, cyclodextrin, one or more in poly(ethylene oxide); Organic system binding agent is selected from: Kynoar, and polytetrafluoroethylene, one or more in polyvinylpyrrolidone, preferably, described binding agent is sodium carboxymethylcellulose and butadiene-styrene rubber compound.
4. a lithium ion battery, comprise can reversible doff lithium positive pole, negative pole and electrolyte, it is characterized in that, negative pole is using tellurium or telluro material claimed in claim 1 as active material, and in described positive pole and negative pole, all comprises binding agent, preferably, in described negative or positive electrode, comprise water-soluble glue as binding agent, particularly preferably, in described positive pole and negative pole, all comprise water-soluble glue as binding agent.
5. lithium ion battery according to claim 4, it is characterized in that: positive electrode is lithium intercalation compound, be selected from lithium transition-metal oxide and polyanion positive electrode, LiMn2O4 and compound thereof, tertiary cathode material and compound thereof, cobalt acid lithium and compound, LiFePO4 and compound thereof, rich lithium material and compound thereof.
6. lithium ion battery according to claim 4, is characterized in that: described binding agent is the combination of water system binding agent or water system binding agent and organic system binding agent; Water system binding agent is selected from: sodium alginate, sodium carboxymethylcellulose, sodium carboxymethylcellulose and butadiene-styrene rubber compound, cyclodextrin, one or more in poly(ethylene oxide); Organic system binding agent is selected from: Kynoar, polytetrafluoroethylene, one or more in polyvinylpyrrolidone.Preferably, described binding agent is sodium carboxymethylcellulose and butadiene-styrene rubber compound; Particularly preferably, in described positive pole and negative pole, all comprise water-soluble glue as binding agent;
Preferably, described conductive additive is selected from Super-P carbon black, Ketjen black, carbon nano-tube, one or more in Graphene, and in described positive pole and negative pole, all comprise conductive additive, also preferably, in described negative or positive electrode, Graphene, Ketjen black and Super-P mixture, as additive, particularly preferably, all comprise Graphene, Ketjen black and Super-P mixture as conductive additive in described positive pole and negative pole;
Preferably, described electrolyte is selected from liquid electrolyte and solid electrolyte;
Wherein, described liquid electrolyte comprises the electrolyte based on protic organic solvent and ionic liquid; Solid electrolyte comprises inorganic solid electrolyte, gel polymer electrolyte and solid polymer electrolyte;
Electrolyte based on protic organic solvent is selected from ether electrolyte and carbonic ester electrolyte; The solvent of ether electrolyte is selected from least one in DOX, glycol dimethyl ether and TRIGLYME, and solute is selected from least one in lithium hexafluoro phosphate, lithium perchlorate, lithium iodide and two (trimethyl fluoride sulfonyl) imine lithium; The solvent of carbonic ester electrolyte 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 lithium hexafluoro phosphate, sodium perchlorate, lithium iodide and two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI);
Described inorganic solid electrolyte is selected from one or more solid-state ceramic electrolyte;
Described polymer dielectric is selected from one or more in the copolymer (PVDF-HFP) of poly(ethylene oxide) (PEO), Polyethylene glycol dimethyl ether (PEGDME), vinylidene fluoride and hexafluoropropylene.
7. prepare the method for lithium ion battery described in claim 4-6 any one for one kind, mainly comprise the steps: using the electrode that contains telluro active material as negative pole, the binding agent that comprises water-soluble glue is as both positive and negative polarity binding agent, comprise Graphene, Ketjen black and Super-P mixture as both positive and negative polarity conductive additive, be assembled into described lithium ion battery.
8. an energy storage elements, is characterized in that: contain the lithium ion battery described in claim 4-6 any one.
9. a portable electric appts, is characterized in that: right to use requires the energy storage elements described in 8.
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