CN103811726A - Preparation method of hollow structure coated positive electrode material - Google Patents

Preparation method of hollow structure coated positive electrode material Download PDF

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CN103811726A
CN103811726A CN201310700828.3A CN201310700828A CN103811726A CN 103811726 A CN103811726 A CN 103811726A CN 201310700828 A CN201310700828 A CN 201310700828A CN 103811726 A CN103811726 A CN 103811726A
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preparation
hollow
core construction
oxide
positive electrode
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CN103811726B (en
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梁兴华
曾帅波
刘于斯
史琳
叶超超
刘天骄
华晓鸣
宋清清
刘浩
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Guangxi University of Science and Technology
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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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • 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
    • H01M4/58—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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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
    • 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

Abstract

The invention discloses a preparation method of a hollow structure coated positive electrode material. The preparation method of the hollow structure coated positive electrode material comprises the following steps: (1) preparing a C/S composite material; (2) preparing a nickel manganese oxide with a hollow structure; and (3) preparing a hollow structure coated positive electrode material. According to the preparation method, the cycle performance of a carbon sulfur composite material is improved by coating the nickel manganese oxide with the hollow structure; the battery positive electrode material provided by the invention can inhibit the self-discharge reaction of a polysulfide, and is combined with O so as to form a chemical bond which is more stable than the Mn-O bond energy to stabilize a nickel manganese acid lithium lattice structure and effectively inhibit the problem of collapse of a nickel manganese acid lithium lattice as Mn3<+> is dissolved into electrolyte, so that the reversible performance of the battery and the capacity retention rate in the cycle process can be improved.

Description

A kind of preparation method of hollow-core construction clad anode material
Technical field
The present invention relates to a kind of cell positive material.
Background technology
The development of portable electronic commnication device is had higher requirement to its chemical power source performance used, especially requires more and more higher to the specific energy of battery.Lithium metal/sulphur battery, its theoretical specific capacity is 1 675 mAh/g-1,, and elemental sulfur positive electrode has advantages such as source is abundant, low price, environmentally friendly, battery security is good, therefore lithium-sulfur cell is considered to the next generation can provide the battery system of the tool 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 is to overcome existing defect, and the hollow-core construction clad anode material that a kind of performance is more superior is provided.
Object of the present invention is carried 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
The mass ratio of nano active charcoal and elemental sulfur being pressed to 1:1 grinding in ball grinder evenly after, put into vacuum drying chamber, pour the about 20min of argon gas, get rid of the air of the inside, and then under mobile nitrogen atmosphere, nano active charcoal and elemental sulfur mixture are heated to 155 ℃, at this temperature, keep 10h, then temperature is elevated to 250 ℃, at this temperature, keeps 3h, 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 is slowly added drop-wise in solution to magnetic agitation 10 minutes, again to the carbon ball adding in this system, with ultrasonic echography until form the state of homogeneous, be transferred to again in reactor 180 ℃ of constant temperature 8 hours, after complete reaction, naturally cool to room temperature, obtain the sediment of black, black precipitate is used respectively to deionized water, absolute ethyl alcohol centrifuge washing three times, remove the impurity of failing to participate in reaction, vacuumize, obtain the presoma of carbon/nickel oxide, presoma is transferred in Muffle furnace, under 600 ℃ of constant temperature, calcine about 4 hours, obtain the Ni, Mn oxide of micron order hollow-core construction,
3) preparation of hollow-core construction clad anode material
By step 2) Ni, Mn oxide that makes is dissolved in absolute ethyl alcohol in the ratio of 1g:16ml, fully stir, obtain after suspension-turbid liquid, regulate pH value to 7.5, C/S composite material is mixed with Ni, Mn oxide solution in the ratio of n (Mn): n (S)=3:200, after stirring, then with deionized water washing, after filtration, in baking oven, dry 10h at 100 ℃, obtains the coated C/S positive electrode of Ni, Mn oxide.
Preferably,, add carbon ball in the ratio of n (Mn): n (C)=3:50.
Preferably, described step 2) in vacuumize, adopt in drying box under 60 ℃ of constant temperature dry 6 hours.
Preferably, in described step 3), adopt and add ammoniacal liquor to regulate pH value.
Beneficial effect of the present invention:
The present invention is by the coated cycle performance that improves carbon sulphur composite material that improves with hollow-core construction Ni, Mn oxide, the self discharge reaction that cell positive material of the present invention suppresses poly sulfide occurs, the formation chemical bond more stable than Mn-O bond energy of being combined with O stablized nickel LiMn2O4 lattice structure, effectively suppresses because of Mn 3+be dissolved in the problem that electrolyte subsides nickel LiMn2O4 lattice, thereby can improve capability retention in the reversibility of battery and cyclic process; Can have and suppress the metal ion of the high valence state oxidation to electrolyte; make electrolyte more stable; can also in certain degree, stop the stripping of Li; when playing protective material stability action, can also improve stability and capability retention in the cyclic process under the conductivity, high temperature of material or under large multiplying power.The advantage having is summarized as follows:
1, high temperature solid-state method of the present invention, its novelty is to use the doping of carbon sulphur composite material, utilizes the space between carbon sulphur better to incorporate raising conductivity.
2, the present invention adopts the coated method of liquid impregnation method, adopts, and energy-conserving and environment-protective more, do not require special process, and without loss of material, cost is low, is easier to industrial production.
What 3, the present invention was prepared is applied to lithium battery by composite material, and 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, for explaining the present invention, is not construed as limiting the invention together with embodiments of the present 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 being 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, only for description and interpretation 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 the mass ratio of 1:1 grinding in ball grinder evenly after, put into vacuum drying chamber, pour the about 20min of argon gas, to get rid of the air of the inside, avoid under high temperature sulphur oxidized.And then under mobile nitrogen atmosphere, active carbon and elemental sulfur mixture are heated to 155 ℃, and at this temperature, keep 10 hours, then temperature is elevated to 250 ℃ of left and right, at this temperature, keep 3h, obtain black product.
2) preparation of hollow-core construction Ni, Mn oxide
The manganese acetate of the nickel acetate of 0.5mol, 1.5mol is dissolved in the absolute ethyl alcohol of 40mL, then concentrated hydrochloric acid was slowly added drop-wise in solution to magnetic agitation about 10 minutes, then to add in this system by n (Mn): n (C)=3:50add carbon ball, use ultrasonic echography until form the state of homogeneous.The product of above-mentioned system is transferred in the reactor of 100mL to 180 ℃ of constant temperature 8 hours.After complete reaction, when naturally cooling to room temperature, obtain the sediment of black.Black precipitate is used respectively to deionized water, absolute ethyl alcohol centrifuge washing three times, remove the impurity of failing to participate in reaction.In vacuum drying chamber, under 60 ℃ of constant temperature, be dried 6 hours, obtain the presoma of carbon/nickel oxide.Presoma is transferred in Muffle furnace, under 600 ℃ of constant temperature, calcined about 4 hours, obtain the Ni, Mn oxide of hollow-core construction.
3) preparation of hollow-core construction clad anode material
By step 2) Ni, Mn oxide that makes is dissolved in deionized water in the ratio of 1g:16ml, after fully stirring, dissolving completely, adds a small amount of ammoniacal liquor, regulates pH value to 7.5.C/S composite material prepared by step 1) mixes with Ni, Mn oxide solution by n (Mn): n (S)=3:200, after stirring, then with deionized water washing, after filtration, in baking oven.At 100 ℃, dry 10h, obtains the coated C/S material of Ni, Mn oxide.
C/S material coated dried Ni, Mn oxide is placed in to chamber type electric resistance furnace, and in air atmosphere, the speed of 3 ℃/min is warming up to 300 ℃, and constant temperature calcining 7h is cooling with stove, obtains hollow-core construction clad anode material.
Electrical Conductivity of Composites of the present invention is as following table:
Figure 846959DEST_PATH_IMAGE001
。
Elemental sulfur, active carbon, composite material, and the XRD figure of carbon sulphur composite material after coated referring to 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 composite material, composite material is that active diffraction envelope when position reduces compared with active carbon near 23 at 2 γ, show to exist and interact between elemental sulfur and active carbon, and illustrate that sulphur is the state of high degree of dispersion in active carbon, this is due in heating process, sulphur steam under elemental sulfur and the high temperature of melting is distributed in the loose structure of active carbon under the higher surface force of active carbon and very strong adsorptivity, before and after coated, 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.
Can cross C/S material is recycled into electric charge and discharge cycles test curve figure (Fig. 2,3) and C/S material before and after coated 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 fast-descending, 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%.Be coated the cycle performance of C/S is improved, the capability retention of the 20th circulation brings up to 90.04% as can be seen here by 82.3% before being coated, and coated 50 capability retentions of circulation are 87%, useful to the raising of C/S sample cycle performance.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in 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
The mass ratio of nano active charcoal and elemental sulfur being pressed to 1:1 grinding in ball grinder evenly after, put into vacuum drying chamber, pour the about 20min of argon gas, get rid of the air of the inside, and then under mobile nitrogen atmosphere, active carbon and elemental sulfur mixture are heated to 155 ℃, at this temperature, keep 10h, then temperature is elevated to 250 ℃, at this temperature, keeps 3h, 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 is slowly added drop-wise in solution to magnetic agitation 10 minutes, again to the carbon ball adding in this system, with ultrasonic echography until form the state of homogeneous, be transferred to again in reactor 180 ℃ of constant temperature 8 hours, after complete reaction, naturally cool to room temperature, obtain the sediment of black, black precipitate is used respectively to deionized water, absolute ethyl alcohol centrifuge washing three times, remove the impurity of failing to participate in reaction, vacuumize, obtain the presoma of carbon/nickel oxide, presoma is transferred in Muffle furnace, under 600 ℃ of constant temperature, calcine about 4 hours, obtain the Ni, Mn oxide of micron-sized hollow-core construction,
3) preparation of hollow-core construction clad anode material
By step 2) Ni, Mn oxide that makes is dissolved in absolute ethyl alcohol in the ratio of 1g:16ml, fully stir, obtain after suspension-turbid liquid, regulate pH value to 7.5, C/S composite material is mixed with Ni, Mn oxide solution in the ratio of n (Mn): n (S)=3:200, after stirring, then with deionized water washing, after filtration, in baking oven, dry 10h at 100 ℃, obtains the coated C/S positive electrode of Ni, Mn oxide.
2. the preparation method of hollow-core construction clad anode material according to claim 1, is characterized in that: described step 2) in, add carbon ball in the ratio of n (Mn): n (C)=3:50.
3. the preparation method of hollow-core construction clad anode material according to claim 1, is characterized in that: described step 2) in vacuumize, adopt in drying box under 60 ℃ 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), adopt and add ammoniacal liquor to regulate pH value.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020110736A1 (en) * 2000-09-25 2002-08-15 Kweon Ho-Jin Positive active material for rechargeable lithium batteries and method for preparing same
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020110736A1 (en) * 2000-09-25 2002-08-15 Kweon Ho-Jin Positive active material for rechargeable lithium batteries and method for preparing same
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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