CN103811726B - A kind of preparation method of hollow-core construction clad anode material - Google Patents
A kind of preparation method of hollow-core construction clad anode material Download PDFInfo
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- CN103811726B CN103811726B CN201310700828.3A CN201310700828A CN103811726B CN 103811726 B CN103811726 B CN 103811726B CN 201310700828 A CN201310700828 A CN 201310700828A CN 103811726 B CN103811726 B CN 103811726B
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention discloses a kind of preparation method of hollow-core construction clad anode material, 1) preparation of C/S composite material; 2) preparation of hollow-core construction Ni, Mn oxide; 3) preparation of hollow-core construction clad anode material.The present invention is by improving with the coated of hollow-core construction Ni, Mn oxide the cycle performance improving carbon sulphur composite material, cell positive material of the present invention suppresses the self discharge reaction of poly sulfide to occur, be combined with O and form the chemical bond more stable than Mn-O bond energy and carry out stable nickel ion doped lattice structure, effectively suppress because of Mn
3+be dissolved in the problem that electrolyte makes nickel ion doped lattice subside, thus capability retention in the reversibility of battery and cyclic process can be improved.
Description
Technical field
The present invention relates to a kind of cell positive material.
Background technology
The chemical power source performance that the development of portable electronic commnication device is used to it is had higher requirement, and especially can require more and more higher to the ratio of battery.Lithium metal/sulphur battery, its theoretical specific capacity is 1675mAh/g-1, and the advantages such as elemental sulfur positive electrode has abundance, low price, environmentally friendly, battery security is good, therefore lithium-sulfur cell is considered to the battery system that the next generation can provide the most potentiality of high specific energy.But because elemental sulfur is typical electronics and ion insulator, the intermediate poly sulfide that reduction process produces is soluble in organic liquid electrolyte, partly soluble poly sulfide diffusion arrives lithium metal anode surface and reacts with its generation self discharge, accelerates the corrosion of lithium, generates unordered Li
2s
2and Li
2s is part irreversible reaction, and this series of problem all causes electrode active material utilance low poor with cycle performance of battery.
Summary of the invention
The technical problem to be solved in the present invention overcomes existing defect, provides the hollow-core construction clad anode material that a kind of performance is more superior.
Object of the present invention carrys out specific implementation by the following technical programs:
A preparation method for hollow-core construction clad anode material,
1) preparation of C/S composite material
Active carbon nanoparticles and elemental sulfur are pressed the mass ratio of 1:1 after grinding in ball grinder is even, put into vacuum drying chamber, pour argon gas and be about 20min, get rid of the air of the inside, and then under the nitrogen atmosphere of flowing, active carbon nanoparticles and elemental sulfur mixture are heated to 155 DEG C, keep 10h at this temperature, then temperature is elevated to 250 DEG C, keeps 3h at this temperature, obtain black C/S composite material;
2) preparation of hollow-core construction Ni, Mn oxide
By nickel acetate, manganese acetate is dissolved in absolute ethyl alcohol according to the mol ratio of 1:3, again concentrated hydrochloric acid to be slowly added drop-wise in solution magnetic agitation 10 minutes, the carbon ball added in this system again, with ultrasonic echography until form homogeneous state, to be transferred in reactor 180 DEG C of constant temperature 8 hours again, after complete reaction, naturally cool to room temperature, obtain the sediment of black, respectively deionized water is used to black precipitate, absolute ethyl alcohol centrifuge washing three times, remove the impurity failing to participate in reaction, vacuumize, obtain the presoma of carbon/nickel oxide, presoma is transferred in Muffle furnace, 4 hours are calcined under 600 DEG C of constant temperature, obtain the Ni, Mn oxide of micron order hollow-core construction,
3) preparation of hollow-core construction clad anode material
By step 2) obtained Ni, Mn oxide is dissolved in absolute ethyl alcohol in the ratio of 1g:16ml, abundant stirring, obtain suspension-turbid liquid after, adjust ph to 7.5, the ratio of C/S composite material in n (Mn): n (S)=3:200 is mixed with Ni, Mn oxide solution, after stirring, then spend deionized water, after filtration, dry 10h at 100 DEG C, obtains the C/S positive electrode that Ni, Mn oxide is coated in an oven.
Preferably, carbon ball is added in the ratio of n (Mn): n (C)=3:50.
Preferably, described step 2) in vacuumize, to adopt in drying box under 60 DEG C of constant temperature dry 6 hours.
Preferably, described step 3) in, adopt and add ammoniacal liquor adjust ph.
Beneficial effect of the present invention:
The present invention is by improving with the coated of hollow-core construction Ni, Mn oxide the cycle performance improving carbon sulphur composite material, cell positive material of the present invention suppresses the self discharge reaction of poly sulfide to occur, be combined with O and form the chemical bond more stable than Mn-O bond energy and carry out stable nickel ion doped lattice structure, effectively suppress because of Mn
3+be dissolved in the problem that electrolyte makes nickel ion doped lattice subside, thus capability retention in the reversibility of battery and cyclic process can be improved; Can have and suppress the metal ion of high-valence state to the oxidation of electrolyte; make electrolyte more stable; the stripping of Li can also be stoped in certain degree; while playing protective material stability action, the stability in the cyclic process under the conductivity of material, high temperature can also be improved or under large multiplying power and capability retention.The advantage had is summarized as follows:
1, high temperature solid-state method of the present invention, its novelty is the doping using carbon sulphur composite material, utilizes the space between carbon sulphur better to incorporate raising conductivity.
2, the present invention adopt liquid-phase impregnation process coated method, adopt, energy-conserving and environment-protective more, do not require special process, and without loss of material, cost is low, is easier to industrial production.
3, be applied to lithium battery by composite material prepared by the present invention, its cycle performance makes moderate progress.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification, together with embodiments of the present invention for explaining the present invention, is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the XRD figure of elemental sulfur, active carbon, composite material and the carbon sulphur composite material after coated;
Fig. 2 is coated front 20 the cycle charge-discharge loop test curve charts of C/S material;
Fig. 3 is coated rear 20 the cycle charge-discharge loop test curve charts of C/S material;
Fig. 4 is coated rear 50 the cycle charge-discharge loop test curve charts of C/S material of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
A preparation method for hollow-core construction clad anode material, comprises the steps:
1) preparation of C/S composite material
By active carbon (analyzing pure) and elemental sulfur (analyzing pure) by 1:1 mass ratio grinding in ball grinder evenly after, put into vacuum drying chamber, pour argon gas and be about 20min, to get rid of the air of the inside, under avoiding high temperature, sulphur is oxidized.And then under the nitrogen atmosphere of flowing, active carbon and elemental sulfur mixture are heated to 155 DEG C, keep 10 hours at this temperature, then temperature is elevated to about 250 DEG C, keeps 3h at this temperature, obtain black product.
2) preparation of hollow-core construction Ni, Mn oxide
The nickel acetate of 0.5mol, the manganese acetate of 1.5mol are dissolved in the absolute ethyl alcohol of 40mL, again concentrated hydrochloric acid is slowly added drop-wise to magnetic agitation about 10 minutes in solution, add in this system again and add carbon ball by n (Mn): n (C)=3:50, with ultrasonic echography until form homogeneous state.The product of above-mentioned system to be transferred in the reactor of 100mL 180 DEG C of constant temperature 8 hours.After complete reaction, when naturally cooling to room temperature, obtain the sediment of black.Deionized water, absolute ethyl alcohol centrifuge washing three times are used respectively to black precipitate, removes the impurity failing to participate in reaction.In vacuum drying chamber under 60 DEG C of constant temperature dry 6 hours, obtain the presoma of carbon/nickel oxide.Presoma is transferred in Muffle furnace, under 600 DEG C of constant temperature, calcine 4 hours, obtain the Ni, Mn oxide of hollow-core construction.
3) preparation of hollow-core construction clad anode material
By step 2) obtained Ni, Mn oxide is dissolved in deionized water in the ratio of 1g:16ml, after fully stirring, dissolving completely, adds a small amount of ammoniacal liquor, adjust ph to 7.5.By step 1) the C/S composite material prepared mixes with Ni, Mn oxide solution by n (Mn): n (S)=3:200, after stirring, then spends deionized water, after filtration, in an oven.Dry 10h at 100 DEG C, obtains the C/S material that Ni, Mn oxide is coated.
C/S material coated for dried Ni, Mn oxide is placed in chamber type electric resistance furnace, the ramp to 300 DEG C of 3 DEG C/min in air atmosphere, constant temperature calcining 7h, with stove cooling, obtains hollow-core construction clad anode material.
Electrical Conductivity of Composites of the present invention is as following table:
| Material | Conductivity |
| The nano-nickel oxide C/S composite material of invention | 6*10 -10S/cm |
| Elemental sulfur | 5*10 -30S/cm |
Elemental sulfur, active carbon, composite material, and the XRD figure of carbon sulphur composite material after coated see Fig. 1, (A represents elemental sulfur, B represents active carbon, C represents C/S composite material, D represents coated C/S composite material), as seen from Figure 1: elemental sulfur exists with amorphous state in the composite, the active diffraction of composite material when 2 γ are position near 23 seals comparatively active carbon and reduces, show to exist between elemental sulfur and active carbon to interact, and illustrate that sulphur is the state of high degree of dispersion in active carbon, this is due in heating process, sulphur steam under the elemental sulfur of melting and high temperature is distributed in the loose structure of active carbon under the higher surface force and very strong adsorptivity of active carbon, coated front and back, the diffraction maximum of sample is basically identical, do not find the diffraction maximum of dephasign, illustrate that coated sample is still pure phase spinel structure.
The coated front and back of C/S material can be crossed be recycled into electric charge and discharge cycles test curve figure (Fig. 2,3) and C/S material for 20 times coated rear to be recycled into electric charge and discharge cycles test curve figure (Fig. 4) for 50 times known: after coated, the cycle performance of C/S sample is improved, especially after 20 circulations, not coated C/S capacity starts quick decline, at the 20th circulation time, capability retention 82.3%.Sample after coated, capacity attenuation amplitude is less, and the capability retention of the 20th circulation still has 93.04%.The cycle performance of the coated C/S of making improves, and the capability retention of the 20th circulation brings up to 90.04% as can be seen here by 82.3% before coated, and coated circulation 50 capability retentions are 87%, useful to the raising of C/S cycles samples performance.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment to invention has been detailed description, for a person skilled in the art, it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. a preparation method for hollow-core construction clad anode material, is characterized in that:
1) preparation of C/S composite material
Active carbon nanoparticles and elemental sulfur are pressed the mass ratio of 1:1 after grinding in ball grinder is even, put into vacuum drying chamber, be filled with argon gas 20min, get rid of the air of the inside, then under the nitrogen atmosphere of flowing, active carbon and elemental sulfur mixture are heated to 155 DEG C, keep 10h at this temperature, then temperature is elevated to 250 DEG C, keeps 3h at this temperature, obtain nanoscale black C/S composite material;
2) preparation of hollow-core construction Ni, Mn oxide
By nickel acetate, manganese acetate is dissolved in absolute ethyl alcohol according to the mol ratio of 1:3, again concentrated hydrochloric acid to be slowly added drop-wise in solution magnetic agitation 10 minutes, the carbon ball added in this system again, with ultrasonic echography until form homogeneous state, to be transferred in reactor 180 DEG C of constant temperature 8 hours again, after complete reaction, naturally cool to room temperature, obtain the sediment of black, respectively deionized water is used to black precipitate, absolute ethyl alcohol centrifuge washing three times, remove the impurity failing to participate in reaction, vacuumize, obtain the presoma of carbon/Ni, Mn oxide, presoma is transferred in Muffle furnace, calcine 4 hours under 600 DEG C of constant temperature, obtain the Ni, Mn oxide of micron-sized hollow-core construction,
3) preparation of hollow-core construction clad anode material
By step 2) obtained Ni, Mn oxide is dissolved in absolute ethyl alcohol in the ratio of 1g:16ml, abundant stirring, obtain suspension-turbid liquid after, adjust ph to 7.5, C/S composite material is mixed with Ni, Mn oxide solution in the ratio that the mol ratio of Mn:S is 3:200, after stirring, then spend deionized water, after filtration, dry 10h at 100 DEG C, obtains the C/S positive electrode that Ni, Mn oxide is coated in an oven; C/S material coated for dried Ni, Mn oxide is placed in chamber type electric resistance furnace, the ramp to 300 DEG C of 3 DEG C/min in air atmosphere, constant temperature calcining 7h, with stove cooling, obtains hollow-core construction clad anode material.
2. the preparation method of hollow-core construction clad anode material according to claim 1, is characterized in that: described step 2) in, the ratio being 3:50 in the mol ratio of Mn:C adds carbon ball.
3. the preparation method of hollow-core construction clad anode material according to claim 1, is characterized in that: described step 2) in vacuumize, to adopt in drying box under 60 DEG C of constant temperature dry 6 hours.
4. the preparation method of hollow-core construction clad anode material according to claim 1, is characterized in that: in described step 3), adopts and adds ammoniacal liquor adjust ph.
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| CN102509803A (en) * | 2011-11-04 | 2012-06-20 | 中山大学 | Preparation method of carbon-coated sulfur anode material of lithium sulfur secondary battery |
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| US6753111B2 (en) * | 2000-09-25 | 2004-06-22 | Samsung Sdi Co., Ltd. | Positive active material for rechargeable lithium batteries and method for preparing same |
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| CN102509803A (en) * | 2011-11-04 | 2012-06-20 | 中山大学 | Preparation method of carbon-coated sulfur anode material of lithium sulfur secondary battery |
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