CN109346684A - A kind of carbon nanotube confined selenium composite cathode material and preparation method thereof - Google Patents
A kind of carbon nanotube confined selenium composite cathode material and preparation method thereof Download PDFInfo
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- CN109346684A CN109346684A CN201811010233.4A CN201811010233A CN109346684A CN 109346684 A CN109346684 A CN 109346684A CN 201811010233 A CN201811010233 A CN 201811010233A CN 109346684 A CN109346684 A CN 109346684A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 125
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 125
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000011669 selenium Substances 0.000 title claims abstract description 86
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010406 cathode material Substances 0.000 title claims 3
- 239000002105 nanoparticle Substances 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract 2
- 238000000227 grinding Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 230000036961 partial effect Effects 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001239 high-resolution electron microscopy Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- MBLUWALPEKUVHJ-UHFFFAOYSA-N [Se].[C] Chemical compound [Se].[C] MBLUWALPEKUVHJ-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000626 liquid-phase infiltration Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
一种碳纳米管限域硒复合正极材料及其制备方法，所述复合正极材料中，单质硒纳米颗粒以质量比0.5～5.0:1限域于碳纳米管一维限域的纳米空间内。所述制备方法，包括以下步骤：（1）将碳纳米管置于强酸中，搅拌下，加热纯化处理，得纯化的碳纳米管；（2）将步骤（1）所得纯化的碳纳米管与硒粉研磨，并充分混合后，在保护性气氛下，低温热处理，得碳纳米管限域硒复合正极材料。本发明碳纳米管限域硒复合正极材料能抑制体积膨胀，和穿梭效应，放电比容量高、高倍率充放电性能及循环性能优异的碳纳米管限域硒复合正极材料；本发明方法工艺简单、成本低廉、适宜于工业化生产。
A carbon nanotube-confined selenium composite positive electrode material and a preparation method thereof. In the composite positive electrode material, elemental selenium nanoparticles are confined in the nano space of carbon nanotube one-dimensional confinement in a mass ratio of 0.5-5.0:1. The preparation method includes the following steps: (1) placing carbon nanotubes in strong acid, stirring, and heating and purifying to obtain purified carbon nanotubes; (2) mixing the purified carbon nanotubes obtained in step (1) with The selenium powder is ground and fully mixed, and then heat-treated at a low temperature in a protective atmosphere to obtain a carbon nanotube confined selenium composite positive electrode material. The carbon nanotube confined selenium composite positive electrode material of the invention can suppress volume expansion and shuttle effect, and has the carbon nanotube confined selenium composite positive electrode material with high discharge specific capacity, high rate charge-discharge performance and excellent cycle performance; the method of the invention is simple , Low cost, suitable for industrial production.
Description
Technical field
The present invention relates to a kind of composite positive poles and preparation method thereof, and in particular to a kind of carbon nanotube confinement selenium is compound
Positive electrode and preparation method thereof.
Background technique
In lithium ion secondary battery system, positive electrode is always the bottleneck for restricting battery development, specific capacity, multiplying power
Performance and cycle performance require further to be promoted.Traditional positive electrode, such as LiCoO2、LiNiO2、LiMn2O4And LiFePO4
Deng, by its theory lithium storage content limited, even if to these positive electrodes carry out ingredient and technique improvement, it is also difficult to make lithium from
Sub- battery makes a breakthrough in energy density.Therefore, develop new high-energy density, long circulation life, excellent multiplying power
The anode material for lithium-ion batteries of performance seems especially urgent and important.
Selenium (Se) is that one kind includes d electronics and the element of the same clan with sulphur (S), since it has up to 3268mAhcm-3
Volume and capacity ratio and 678 mAhg-1Specific discharge capacity, and the electrical conductance (1 × 10 much higher than S-3S·m-1), Se quilt
It is considered a kind of potential anode material for lithium-ion batteries with high capacity and excellent high rate performance, has caused vast research work
The extensive research interest of person.But Se and Li occurs that big volume expansion can be generated when electrochemical reaction, and same as S electrode
With shuttle effect.When carrying out charge discharge, the Li of Se and insertion anode react, and it is more to generate soluble interphase
Selenides (Li2Sex, 3≤x≤8), on the one hand which, can be dissolved in the loss that positive electrode active material is caused in electrolyte, separately
On the one hand, cathode, and the solid-state passivation layer of the Surface Creation non-solubility in cathode can be reached by electrolyte, cause cathode living
The failure of property object, eventually leads to biggish irreversible capacity loss and capacity attenuation, shows poor cyclical stability.Cause
This, how to slow down capacity attenuation is the key that improve Li-Se secondary cell chemical property.
CN101864316A discloses a kind of carbon nanotube/cadmium selenide quantum dot nano composite material and preparation method, should
For carbon nanotube/cadmium selenide quantum dot nano composite material using carbon nanotube as skeleton, surface coats CdSe quantum dots.But
The composite material only uses carbon nanotube as the timbering material of selenizing cadmium material, and cadmium selenide is not introduced into carbon nanotube
Portion, still without solving the problems, such as irreversible capacity loss caused by volume expansion and capacity attenuation in cyclic process.
CN102553528A discloses a kind of modified carbon nano tube tube material, goes to the method for mercury ion and its regeneration side in water removal
Method, the modified carbon nano tube tube material is that selenium modifies nanometer particle load/ferriferous oxide magnetic carbon-nano tube composite material, by it
As adsorbent, it is placed in pending water to adsorb mercury ion in water.But the selenium in the modified carbon nano tube tube material is equally
Be intended only as the surfactant of carbon nanotube, do not enter inside carbon nanotube, and itself and be not used for as battery material.
CN104201349A discloses a kind of preparation method of selenium carbon electrode material with porous structure, and this method is by carbon
Material is introduced into selenium positive electrode, but it is swollen simultaneously to solve volume of the selenium positive electrode in charge and discharge process to the full extent
Swollen problem.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of energy inhibition
Volume expansion and shuttle effect, the carbon nanotube confinement that specific discharge capacity is high, high-rate charge-discharge capability and cycle performance are excellent
Selenium composite positive pole.
The further technical problems to be solved of the present invention are to overcome drawbacks described above of the existing technology, provide a kind of work
The preparation method of skill carbon nanotube confinement selenium composite positive pole that is simple, low in cost, being suitable for industrialized production.
The technical solution adopted by the present invention to solve the technical problems is as follows: a kind of carbon nanotube confinement selenium anode composite material
Expect, in the composite positive pole, elemental selenium nano particle is with 0.5~5.0:1 of mass ratio confinement in the one-dimensional confinement of carbon nanotube
Nano-space in.Carbon nanotube confinement selenium composite positive pole of the present invention by by selenium confinement in the one-dimensional confinement of carbon nanotube
Nano-space in, on the one hand, can greatly enhance its electrical conductance and inhibit or the volume expansion that is induced of carrying lithiumation；Separately
On the one hand, by the limitation of nano aperture and adsorption effect, soluble more selenium intermediate products can be fixed up, to reach
To the purpose for inhibiting shuttle effect.Particle is entered pipeline and then formed a variety of orderly by package in the forming process of rigid pipe
Structure, i.e., one-dimensional confinement structure.
Preferably, the diameter of the carbon nanotube is 5~30 nm.
Preferably, the partial size of the elemental selenium nano particle is 5~20 nm, and elemental selenium nano particle is less than institute's confinement
Carbon nanotube diameter.
The present invention further solves technical solution used by its technical problem: a kind of carbon nanotube confinement selenium is compound just
The preparation method of pole material, comprising the following steps:
(1) carbon nanotube is placed in strong acid, under stirring, heating purified processing obtains the carbon nanotube of purifying；
(2) carbon nanotube and selenium powder that will be purified obtained by step (1) are ground, and after being sufficiently mixed, under protective atmosphere, low temperature
Heat treatment, obtains carbon nanotube confinement selenium composite positive pole.
Preferably, in step (1), the temperature of the heating purified processing is 50~200 DEG C, and the time is 1~10 h.Acid adding
The purpose of processing is the impurity removed in carbon nanotube.The heating purified preferred oil bath of processing.If heating purified temperature mistake
The low or time is too short, then purifying not exclusively, still can the impurity such as residual amorphous carbon, carbon nanotube particle or catalyst granules,
If heating purified temperature is excessively high or overlong time, the structure of carbon nanotube can be destroyed.
Preferably, in step (1), the mass volume ratio (g/mL) of the carbon nanotube and strong acid is 1~8:100.If strong
Sour dosage is excessive, then can destroy the structure of carbon nanotube, if strong acid dosage is very few, purifying is not thorough, still can residual impurity.
Preferably, in step (1), the strong acid is one or more of the concentrated sulfuric acid, concentrated nitric acid or concentrated hydrochloric acid etc..It is described
The mass fraction of the concentrated sulfuric acid is 70~100%, and the mass fraction of the concentrated nitric acid is 68~97.5%, the quality point of the concentrated hydrochloric acid
Number is 20~40%.
Preferably, in step (2), the mass ratio of the carbon nanotube and selenium powder is 1:0.5~5.0.If carbon nanotube is used
It measures very few, then cannot accommodate all selenium powders, if carbon nanotube dosage is excessive, can cannot provide charge and discharge because of carbon nanotube
Capacity can reduce the capacity of entire electrode.
Preferably, in step (2), the revolving speed of the grinding is 50~500 r/min, and the time is 0.5~10 h.Grinding
Purpose also can be improved the surface-active of carbon nanotube, melt infiltration convenient for later period selenium powder other than being uniformly mixed.
Preferably, in step (2), the Low Temperature Heat Treatment refers to: from room temperature, being warming up to the rate of 2~8 DEG C/min
200~300 DEG C, keep the temperature 1~8 h.Selenium has lower fusing point, and after heat treatment reaches certain temperature, selenium powder will be with liquid
Form enter inside carbon nanotube, to form the composite material of carbon nanotube confinement selenium.
Preferably, in step (2), the protective atmosphere is argon gas and/or nitrogen.Protectiveness gas used in the present invention
Atmosphere is the high-purity gas of purity >=99.9%.
Beneficial effects of the present invention are as follows:
(1) in carbon nanotube confinement selenium composite positive pole of the present invention, the confinement of elemental selenium nano particle is in the one-dimensional limit of carbon nanotube
In the nano-space in domain, the diameter of carbon nanotube is 5~30 nm, and the partial size of the elemental selenium nano particle is 5~20 nm, can
It is novel high-performance electrode to be effectively improved specific discharge capacity and cycle performance effectively to enhance its electrochemical lithium storage performance
The exploitation and research of material provide new thinking；
(2) Electrochemical Properties show carbon nanotube confinement selenium composite positive pole of the present invention in the mA/g of 1C(1C=678)
Current density under, discharge capacity may be up to 185 mAhg for the first time-1；In the mA/g of 10 C(1C=678) current density under,
Specific discharge capacity may be up to 92 mAhg-1, after circulation 100 is enclosed, specific discharge capacity remains at 54 mAhg-1, illustrate due to
The volume expansion of the presence of carbon nanotube, selenium is inhibited well, and lithium storage performance is improved, so as to improve battery
Circulation and high rate performance；
(3) present invention process it is simple, it is low in cost, be suitable for industrialized production.
Detailed description of the invention
Fig. 1 is the high resolution electron microscopy transmission plot EDS power spectrum of 1 carbon nanotube confinement selenium composite positive pole of the embodiment of the present invention
Analysis chart；
Fig. 2 is the low power transmission electron microscope picture of 1 carbon nanotube confinement selenium composite positive pole of the embodiment of the present invention；
Fig. 3 is the high resolution electron microscopy transmission plot of 1 carbon nanotube confinement selenium composite positive pole of the embodiment of the present invention；
Fig. 4 is 1 carbon nanotube confinement selenium composite positive pole of the embodiment of the present invention and 1 carbon nanotube of comparative example/selenium anode composite
The charge-discharge performance test comparison chart of the battery of material assembling.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Carbon nanotube used in the embodiment of the present invention is purchased from Sigma-Aldrich；Used in the embodiment of the present invention
Argon gas, nitrogen are the high-purity gas of purity >=99.9%；Chemical reagent used in the embodiment of the present invention, unless otherwise specified,
Obtained by routine business approach.
A kind of carbon nanotube confinement selenium composite positive pole embodiment 1
In the composite positive pole, elemental selenium nano particle is with mass ratio 4:1 confinement in the nanometer of the one-dimensional confinement of carbon nanotube
In space；The diameter of the carbon nanotube is 5~20nm；The partial size of the elemental selenium nano particle is 5~10 nm, and simple substance
Selenium nano particle is less than the diameter of the carbon nanotube of institute's confinement.
As shown in Figure 1, containing selenium, carbon in carbon nanotube confinement selenium composite positive pole of the embodiment of the present invention, and not
Contain impurity (when EDS is detected, sample is placed in copper micro-grid, so show copper, not impurity).
As shown in Fig. 2, carbon nanotube is evenly distributed in carbon nanotube confinement selenium composite positive pole of the embodiment of the present invention,
Agglomeration is had no, the diameter of carbon nanotube is 5~20nm.
As shown in figure 3, selenium nano particle is limited in carbon nanotube confinement selenium composite positive pole of the embodiment of the present invention
In in the nano-space of the one-dimensional confinement of carbon nanotube, the partial size of elemental selenium nano particle is 5~10nm in domain.
A kind of preparation method embodiment 1 of carbon nanotube confinement selenium composite positive pole
(1) 3 g carbon nanotubes are placed in strong acid (concentrated sulfuric acid of 40 mL mass fractions 98% is dense with 120 mL mass fractions 97%
The mixed acid of nitric acid) in, under stirring, at 130 DEG C, oil bath heating purification process 8h obtains the carbon nanotube of 2.4 g purifying；
(2) by the carbon nanotube and 8g selenium powder of the purifying of 2g obtained by step (1), in the agate mortar, under 400 r/min, grinding
4h, and after being sufficiently mixed, under an argon atmosphere, from room temperature, 260 DEG C is warming up to the rate of 5 DEG C/min, 6 h is kept the temperature, obtains carbon
Nanotube confinement selenium composite positive pole.
The assembling of battery: by carbon nanotube of embodiment of the present invention confinement selenium composite positive pole and carbon black and sodium alginate with
The mass ratio of 8:1:1, and using water as solvent mixed grinding, then it is uniformly applied to aluminium foil surface, it is multiple to obtain carbon nanotube confinement selenium
Close positive electrode smear；Then, in the closed glove box of applying argon gas, it is with carbon nanotube confinement selenium composite positive pole smear
Anode, metal lithium sheet are cathode, and microporous polypropylene membrane is as diaphragm, the LiPF of 1.0mol/L6Being dissolved in volume ratio is 1:1:1
Ethylene carbonate, dimethyl carbonate and dimethyl carbonate in the mixed solvent as electrolyte, be assembled into the button of CR2025
Formula battery carries out charge-discharge test.
As shown in figure 4, the battery of carbon nanotube confinement selenium composite positive pole of embodiment of the present invention assembling, in 1~3V electricity
Press in range, the mA/g of 1C(1C=678) current density (preceding two circle) under, discharge capacity may be up to 185 mAhg for the first time-1；
In the mA/g of 10 C(1C=678) current density (since third circle) under, specific discharge capacity may be up to 92 mAhg-1, follow
After ring 100 encloses, specific discharge capacity remains at 54 mAhg-1, illustrate that the presence due to carbon nanotube, the volume expansion of selenium obtain
Inhibit to good, lithium storage performance is improved, so as to improve the circulation and high rate performance of battery.
A kind of carbon nanotube confinement selenium composite positive pole embodiment 2
In the composite positive pole, elemental selenium nano particle is with mass ratio 3:2 confinement in the nanometer of the one-dimensional confinement of carbon nanotube
In space；The diameter of the carbon nanotube is 20~25nm；The partial size of the elemental selenium nano particle is 10~15nm, and simple substance
Selenium nano particle is less than the diameter of the carbon nanotube of institute's confinement.
Through detecting, selenium, carbon are contained in carbon nanotube confinement selenium composite positive pole of the embodiment of the present invention, and do not contain
Impurity.
Through detecting, in carbon nanotube confinement selenium composite positive pole of the embodiment of the present invention, carbon nanotube is evenly distributed, and has no
Agglomeration, the diameter of carbon nanotube are 20~25nm.
Through detecting, in carbon nanotube confinement selenium composite positive pole of the embodiment of the present invention, selenium nano particle is by confinement
In in the nano-space of the one-dimensional confinement of carbon nanotube, the partial size of elemental selenium nano particle is 10~15nm.
A kind of preparation method embodiment 2 of carbon nanotube confinement selenium composite positive pole
(1) 5g carbon nanotube is placed in strong acid (concentrated sulfuric acid of 40 mL mass fraction, 70 % is dense with 120 mL mass fractions 68%
The mixed acid of nitric acid) in, under stirring, at 80 DEG C, oil bath heating purification process 10h obtains the carbon nanotube of 4.8 g purifying；
(2) by the carbon nanotube and 6g selenium powder of the purifying of 4g obtained by step (1), in the agate mortar, under 200 r/min, grinding 1
H, and after being sufficiently mixed, under an argon atmosphere, from room temperature, 200 DEG C is warming up to the rate of 2 DEG C/min, 8h is kept the temperature, obtains carbon and receive
Mitron confinement selenium composite positive pole.
The assembling of battery: with embodiment 1.
Through detecting, the battery of carbon nanotube confinement selenium composite positive pole of embodiment of the present invention assembling, in 1~3V voltage model
In enclosing, the mA/g of 1C(1C=678) current density (preceding two circle) under, discharge capacity may be up to 178 mAhg for the first time-1；10
The mA/g of C(1C=678) current density (since third circle) under, specific discharge capacity may be up to 89 mAhg-1, circulation 100
After circle, specific discharge capacity remains at 53 mAhg-1, illustrate that the presence due to carbon nanotube, the volume expansion of selenium obtain very well
Inhibition, lithium storage performance is improved, so as to improve the circulation and high rate performance of battery.
A kind of carbon nanotube confinement selenium composite positive pole embodiment 3
In the composite positive pole, elemental selenium nano particle is with mass ratio 2:3 confinement in the nanometer of the one-dimensional confinement of carbon nanotube
In space；The diameter of the carbon nanotube is 25~30 nm；The partial size of the elemental selenium nano particle is 15~20 nm, and single
Matter selenium nano particle is less than the diameter of the carbon nanotube of institute's confinement.
Through detecting, selenium, carbon are contained in carbon nanotube confinement selenium composite positive pole of the embodiment of the present invention, and do not contain
Impurity.
Through detecting, in carbon nanotube confinement selenium composite positive pole of the embodiment of the present invention, carbon nanotube is evenly distributed, and has no
Agglomeration, the diameter of carbon nanotube are 25~30 nm.
Through detecting, in carbon nanotube confinement selenium composite positive pole of the embodiment of the present invention, selenium nano particle is by confinement
In in the nano-space of the one-dimensional confinement of carbon nanotube, the partial size of elemental selenium nano particle is 15~20 nm.
A kind of preparation method embodiment 3 of carbon nanotube confinement selenium composite positive pole
(1) 5g carbon nanotube is placed in strong acid (concentrated sulfuric acid of 40 mL mass fraction, 82 % is dense with 80 mL mass fraction, 30 %'s
The mixed acid of hydrochloric acid) in, under stirring, at 180 DEG C, oil bath heating purification process 6h obtains the carbon nanotube of 4.8g purifying；
(2) by the carbon nanotube and 4g selenium powder of the purifying of 6g obtained by step (1), in the agate mortar, under 500 r/min, grinding 8
H, and after being sufficiently mixed, in a nitrogen atmosphere, from room temperature, 300 DEG C is warming up to the rate of 8 DEG C/min, 4h is kept the temperature, obtains carbon and receive
Mitron confinement selenium composite positive pole.
The assembling of battery: with embodiment 1.
Through detecting, the battery of carbon nanotube confinement selenium composite positive pole of embodiment of the present invention assembling, in 1~3V voltage model
In enclosing, the mA/g of 1C(1C=678) current density (preceding two circle) under, discharge capacity may be up to 176 mAhg for the first time-1；10
The mA/g of C(1C=678) current density (since third circle) under, specific discharge capacity may be up to 85 mAhg-1, circulation 100
After circle, specific discharge capacity remains at 48 mAhg-1, illustrate that the presence due to carbon nanotube, the volume expansion of selenium obtain very well
Inhibition, lithium storage performance is improved, so as to improve the circulation and high rate performance of battery.
Carbon nanotube/selenium composite positive pole comparative example 1
(1) with embodiment 1；
(2) by the carbon nanotube and 8g selenium powder of the purifying of 2g obtained by step (1), in the agate mortar, under 400 r/min, grinding 4
H, and after being sufficiently mixed, obtain carbon nanotube/selenium composite positive pole.
The assembling of battery: with embodiment 1.
As shown in figure 4, this comparative example carbon nanotube/selenium composite positive pole assembling battery, in 1~3V voltage range
Interior, the mA/g of 1C(1C=678) current density (preceding two circle) under, discharge capacity only 40 mAhg for the first time-1；10 C(1C=
678 mA/g) current density (since third circle) under, specific discharge capacity only 18 mAhg-1, after circulation 100 is enclosed, discharge ratio
Capacity only 12 mAhg-1, illustrate selenium powder in the case where no any material is protected, can directly it is exposed in the electrolytic solution, cause
Material dissolution falls off in the electrolytic solution or directly, so that specific discharge capacity is reduced rapidly；With the embodiment of the present invention 1~3
The battery of gained carbon nanotube confinement selenium composite positive pole assembling is compared, and very poor chemical property is shown.
Claims (8)
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