CN103762366B - A kind of carbon nano-tube combination electrode preparation method - Google Patents

A kind of carbon nano-tube combination electrode preparation method Download PDF

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Publication number
CN103762366B
CN103762366B CN201310604266.2A CN201310604266A CN103762366B CN 103762366 B CN103762366 B CN 103762366B CN 201310604266 A CN201310604266 A CN 201310604266A CN 103762366 B CN103762366 B CN 103762366B
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carbon nano
tubes
electrode
walled carbon
combination electrode
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CN103762366A (en
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范茂松
金翼
官亦标
马小航
丁楚雄
陈春华
来小康
郭剑波
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University of Science and Technology of China USTC
State Grid Corp of China SGCC
China Electric Power Research Institute Co Ltd CEPRI
State Grid Anhui Electric Power Co Ltd
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University of Science and Technology of China USTC
State Grid Corp of China SGCC
China Electric Power Research Institute Co Ltd CEPRI
State Grid Anhui Electric Power Co Ltd
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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 present invention relates to a kind of carbon nano-tube combination electrode preparation method, described method comprises: (1) preparation manganese acetate solution; (2) preliminary treatment is carried out to multi-walled carbon nano-tubes; (3) pour described manganese acetate solution into multi-walled carbon nano-tubes and obtain precursor liquid; (4) regulate direct voltage and underlayer temperature, substrate deposits, before deposition starts, pre-logical nitrogen, sinters after preparing film in a nitrogen atmosphere, obtained manganese oxide/multi-walled carbon nano-tubes composite film electrode.Present invention achieves the preparation of manganese oxide/multi-walled carbon nano-tubes combination electrode, the electrode of different carbon nano-tube adding proportion can be prepared; Electrode prepared by the present invention decreases the use of other conductive carbon material and collector in battery, can lower carbon nano-tube use cost in the battery; Electrode quality prepared by the present invention is lighter, improves the energy density of electrode; Electrode conductivuty prepared by the present invention is better, has widened the application of electrode.

Description

A kind of carbon nano-tube combination electrode preparation method
Technical field
The invention belongs to battery energy storage technology, specifically relate to a kind of carbon nano-tube combination electrode preparation method.
Background technology
Short commentary article within 1997, is had to point out that carbon nano-tube can apply in lithium ion battery electrode material, and real research carbon nano-tube being replaced conventional material with carbon element as lithium ion battery negative material of just having occurred for 1999 after two years, so far after, the application of carbon nano-tube in lithium-ion battery system enters the fast-developing stage, use from the early stage negative material that directly does, use to as positive electrode and cathode material conductive agent or conductive additive, or as using without collector electrode substrate, research up to date finds the modification by carrying out specific functional groups to carbon nano-tube, carbon nano-tube can use as a kind of special positive electrode equally.
The not same-action that carbon nano-tube plays in lithium-ion battery system, first be as conductive agent or conductive agent additive, why carbon nano-tube can be applied as conductive component, mainly specific to it physical property determine, carbon nano-tube is relative to other conductive carbon materials, have higher conductance, indoor temperature measurement can reach 5 × 105 s/ m, simultaneously as a kind of special monodimension nanometer material, it has very high draw ratio (>10000), mean under less mixed ratio, can be just that electrode material obtains good conductive effect, for other conductive carbon materials, can effectively reduce conductive agent consumption, thus indirectly improve the load capacity of active material in unit volume, and then improve the energy of monomer lithium ion battery.And carbon nano-tube has the characteristic of chirality π Orbital Overlap, can radially transmit with micron-sized mean free path when electronics transmits therein, this characteristic can the high rate performance of active electrode material, has very important significance for practical application tool.In conductive agent application aspect, carbon nano-tube can apply to different electrode materials, as LiCoO in positive electrode 2, LiMn 2o 4, LiNi 0.8co 0.2o 2, LiFePO 4, Li 3v 2(PO 4) 3, LiNi 0.45al 0.05mn 1.5o 4, LiCo 0.5mn 0.5pO 4deng, as Co in negative material 3o 4, CoO, Li 4ti 5o 12, SnO 2, CoFe 2o 4deng, no matter for positive electrode or negative material, carbon nano-tube is introduced as conductive agent wherein can form good conductive network, is conducive to the transmission of electronics, therefore the electrode material prepared often has excellent large high rate performance, and long circulating stability is also improved.
Carbon nano-tube is done without collector combination electrode as the another kind of form that conductive agent uses exactly, not there is no collector without collector electrode, but the film utilizing carbon nano-tube to prepare replaces conventional collector (Copper Foil or aluminium foil), electrode material is compounded among carbon nano-tube film by this form main implementation exactly, such carbon nano-tube film also can as collector while serving as conductive agent, therefore the use of other conductive carbon materials and conventional collector can be reduced, and it is better that Film laminated electrode has conductivity relative to conventional collector electrode, quality is lighter, the better feature of pliability, can the application of open lithium ion battery, the more important thing is relative to traditional lithium-ion battery, contained active material Quality advance in the battery unit volume of Film laminated, cell integrated energy density also significantly improves.
Except utilizing its conduction property, appearing at the earliest in lithium ion battery of carbon nano-tube replaces conventional material with carbon element to use using direct as negative material, relative to ordinary graphite negative pole, its theoretical specific capacity of carbon nanometer tube negative pole material is more than 1116mAh/g, much larger than the 372mAh/g of graphite cathode, so high capacity is mainly because except carbon nano-tube carbocyclic ring storage lithium own, there is a large amount of defect in its tubular structure, the position of removal lithium embedded can be provided, and also can store up lithium between carbon nano-tube carbon-coating.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of carbon nano-tube combination electrode preparation method, the method with manganese acetate and multi-walled carbon nano-tubes for raw material, by electrostatic spray precipitation equipment, grope the state modulator in preparation process, successfully prepare manganese acetate/multi-walled carbon nano-tubes combination electrode.It is better that this Film laminated electrode has conductivity relative to conventional collector electrode, quality is lighter, the better feature of pliability, can the application of open lithium ion battery, simultaneously, relative to traditional lithium-ion battery, contained active material Quality advance in the battery unit volume of Film laminated, cell integrated energy density also significantly improves.
The object of the invention is to adopt following technical proposals to realize:
A kind of carbon nano-tube combination electrode preparation method, its improvements are, described method comprises:
(1) manganese acetate solution is prepared;
(2) preliminary treatment is carried out to multi-walled carbon nano-tubes;
(3) pour described manganese acetate solution into multi-walled carbon nano-tubes and obtain precursor liquid;
(4) regulate direct voltage and underlayer temperature, substrate deposits, before deposition starts, pre-logical nitrogen, sinters after preparing film in a nitrogen atmosphere, obtained manganese oxide/multi-walled carbon nano-tubes composite film electrode.
Preferably, described step (1) comprises with 1.2-propylene glycol for solvent, is dissolved in 1.2-propylene glycol solvent by manganese acetate and carries out adding thermal agitation at 65 DEG C.
Preferably, described step (2) to comprise with the concentrated sulfuric acid and red fuming nitric acid (RFNA) mixed solution for cleaning fluid, stirs back and heat up in a steamer at 65 DEG C, for subsequent use after eccentric cleaning, for improving the dispersiveness of multi-walled carbon nano-tubes in aqueous phase.
Further, the concentrated sulfuric acid and red fuming nitric acid (RFNA) volume ratio 1:1 is chosen as in the described concentrated sulfuric acid and red fuming nitric acid (RFNA) mixed solution.
Preferably, described step (3) comprises the multi-walled carbon nano-tubes dispersion after by cleaning in deionized water, carries out ultrasonic disperse, is poured in described manganese acetate solution, stir ultrasonic rear obtained precursor liquid.
Further, in described precursor liquid, the concentration of manganese acetate is 5-15mM, and the additional proportion of multi-walled carbon nano-tubes takes with the percentage of manganese acetate quality used, and the adding proportion selected is being respectively between 0wt% ~ 20wt%.
Preferably, it is substrate that described step (4) comprises employing nickel foam, regulate direct voltage and underlayer temperature, after voltage and temperature reach, described precursor liquid deposits on substrate, and before deposition starts, pre-logical nitrogen, keeps nitrogen atmosphere in whole process, sinter in a nitrogen atmosphere after preparing film, obtained manganese oxide/multi-walled carbon nano-tubes composite film electrode.
Compared with the prior art, beneficial effect of the present invention is:
1, present invention achieves the preparation of manganese oxide/multi-walled carbon nano-tubes combination electrode, the electrode of different carbon nano-tube adding proportion can be prepared.
2, the electrode that prepared by the present invention decreases the use of other conductive carbon material and collector in battery, can lower carbon nano-tube use cost in the battery.
3, the electrode quality prepared of the present invention is lighter, improves the energy density of electrode.
4, the electrode conductivuty prepared of the present invention is better, has widened the application of electrode.
Accompanying drawing explanation
Fig. 1 is a kind of carbon nano-tube combination electrode preparation method schematic diagram provided by the invention.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
The manganese source that preparation process uses is manganese acetate Mn (Ac) 2.4H 2o take multi-walled carbon nano-tubes as carbon source, electrostatic spray depositing device used be the exploitation of laboratory designed, designed can the sprayer unit of the lower work of nitrogen atmosphere protection, device is as shown in Figure 1.
Specific experiment flow process is as follows:
(1) with 1.2-propylene glycol for solvent, first manganese acetate is dissolved in 1.2-propylene glycol solvent at 65 DEG C, then carries out adding thermal agitation.
(2) first preliminary treatment is carried out to multi-walled carbon nano-tubes, with the concentrated sulfuric acid and red fuming nitric acid (RFNA) mixed solution for cleaning fluid, stir back at 65 DEG C and heat up in a steamer, for subsequent use after eccentric cleaning, to improve the dispersiveness of multi-walled carbon nano-tubes in aqueous phase.
(3) by the multi-walled carbon nano-tubes dispersion after cleaning in deionized water, carry out ultrasonic disperse, be poured into the above-mentioned manganese acetate solution prepared again, stir ultrasonic, obtained precursor liquid, in final precursor liquid, the concentration of manganese acetate is 5-15mM, and the additional proportion of multi-walled carbon nano-tubes takes with the percentage of manganese acetate quality used, and the adding proportion selected is being respectively between 0wt% ~ 20wt%.
(4) take nickel foam as substrate, regulate direct voltage and underlayer temperature, after voltage and temperature reach, precursor liquid deposits on substrate, pre-logical nitrogen before deposition starts, keep nitrogen atmosphere in whole process, sinter in a nitrogen atmosphere after preparing film, obtained manganese oxide/multi-walled carbon nano-tubes composite film electrode.
Embodiment
(1) with 1.2-propylene glycol for solvent, first manganese acetate is dissolved in (50ml) in 1.2-propylene glycol solvent at 65 DEG C, adds thermal agitation 2 hours.
(2) first preliminary treatment is carried out to multi-walled carbon nano-tubes, with the concentrated sulfuric acid and red fuming nitric acid (RFNA) (volume ratio 1:1) mixed solution for cleaning fluid, stir back at 65 DEG C and heat up in a steamer 10 hours, for subsequent use after eccentric cleaning, to improve the dispersiveness of multi-walled carbon nano-tubes in aqueous phase.
(3) by the multi-walled carbon nano-tubes dispersion after cleaning in deionized water (10ml), ultrasonic disperse 0.5 hour, be poured into the above-mentioned manganese acetate solution prepared again, stir ultrasonic each 0.5 hour, obtained precursor liquid, in final precursor liquid, the concentration of manganese acetate is 10mM, and the additional proportion of multi-walled carbon nano-tubes takes with the percentage of manganese acetate quality used, and the adding proportion selected is 5wt%.
(4) take nickel foam as substrate, direct voltage ~ 8.5KV, underlayer temperature is 250 DEG C, sedimentation time is 2.5 hours, before deposition starts, pre-logical nitrogen 30 minutes, keeps nitrogen atmosphere in experimentation, prepares after film at 500 DEG C, 5 hours are sintered, obtained manganese oxide/multi-walled carbon nano-tubes composite film electrode under nitrogen atmosphere.
Finally should be noted that: above embodiment is only in order to illustrate that technical scheme of the present invention is not intended to limit, although with reference to above-described embodiment to invention has been detailed description, those of ordinary skill in the field are to be understood that: still can modify to the specific embodiment of the present invention or equivalent replacement, and not departing from any amendment of spirit and scope of the invention or equivalent replacement, it all should be encompassed in the middle of right of the present invention.

Claims (7)

1. a carbon nano-tube combination electrode preparation method, is characterized in that, described method comprises:
(1) manganese acetate solution is prepared;
(2) with the concentrated sulfuric acid and red fuming nitric acid (RFNA) mixed solution for cleaning fluid, preliminary treatment is carried out to multi-walled carbon nano-tubes;
(3) multi-walled carbon nano-tubes after step (2) being processed is scattered in deionized water, poured into by the dispersion liquid of multi-walled carbon nano-tubes in the described manganese acetate solution of step (1) and obtain precursor liquid, in described precursor liquid, the concentration of manganese acetate is 5-15mM;
(4) regulate direct voltage and underlayer temperature, substrate deposits, before deposition starts, pre-logical nitrogen, sinters after preparing film in a nitrogen atmosphere, obtained manganese oxide/multi-walled carbon nano-tubes composite film electrode.
2. a kind of carbon nano-tube combination electrode preparation method as claimed in claim 1, is characterized in that, it is solvent that described step (1) comprises with 1,2-PD, is dissolved in 1,2-PD solvent by manganese acetate and carries out adding thermal agitation at 65 DEG C.
3. a kind of carbon nano-tube combination electrode preparation method as claimed in claim 1, is characterized in that, described step (2) stirs back at 65 DEG C heats up in a steamer, for subsequent use after eccentric cleaning, for improving the dispersiveness of multi-walled carbon nano-tubes in aqueous phase.
4. a kind of carbon nano-tube combination electrode preparation method as claimed in claim 3, is characterized in that, is chosen as the concentrated sulfuric acid and red fuming nitric acid (RFNA) volume ratio 1:1 in the described concentrated sulfuric acid and red fuming nitric acid (RFNA) mixed solution.
5. a kind of carbon nano-tube combination electrode preparation method as claimed in claim 1, it is characterized in that, in described step (3) by the multi-walled carbon nano-tubes dispersion after cleaning in deionized water, carry out ultrasonic disperse, be poured in described manganese acetate solution, stir ultrasonic rear obtained precursor liquid.
6. a kind of carbon nano-tube combination electrode preparation method as claimed in claim 5, is characterized in that, the additional proportion of described multi-walled carbon nano-tubes takes with the percentage of manganese acetate quality used, and the adding proportion selected is between 5wt% ~ 20wt%.
7. a kind of carbon nano-tube combination electrode preparation method as claimed in claim 1, it is characterized in that, it is substrate that described step (4) comprises employing nickel foam, regulate direct voltage and underlayer temperature, after voltage and temperature reach, described precursor liquid deposits on substrate, pre-logical nitrogen before deposition starts, keep nitrogen atmosphere in whole process, sinter in a nitrogen atmosphere after preparing film, obtained manganese oxide/multi-walled carbon nano-tubes composite film electrode.
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CN109830649B (en) * 2019-01-14 2021-10-26 湘潭大学 Preparation process of flexible electrode with long cycle life and high specific capacity

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060061412A (en) * 2004-12-02 2006-06-08 현대자동차주식회사 Method for manufacturing manganese oxide/carbon nanotube composite electrode for super capacitor using electrostatic spary deposition
CN1790783A (en) * 2004-11-26 2006-06-21 三星Sdi株式会社 Electrode for fuel cell, fuel cell comprising the same, and method for preparing the same
US7986509B2 (en) * 2008-01-17 2011-07-26 Fraser Wade Seymour Composite electrode comprising a carbon structure coated with a thin film of mixed metal oxides for electrochemical energy storage
US8493711B2 (en) * 2008-01-17 2013-07-23 Fraser W. SEYMOUR Monolithic electrode, related material, process for production, and use thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1790783A (en) * 2004-11-26 2006-06-21 三星Sdi株式会社 Electrode for fuel cell, fuel cell comprising the same, and method for preparing the same
KR20060061412A (en) * 2004-12-02 2006-06-08 현대자동차주식회사 Method for manufacturing manganese oxide/carbon nanotube composite electrode for super capacitor using electrostatic spary deposition
US7986509B2 (en) * 2008-01-17 2011-07-26 Fraser Wade Seymour Composite electrode comprising a carbon structure coated with a thin film of mixed metal oxides for electrochemical energy storage
US8493711B2 (en) * 2008-01-17 2013-07-23 Fraser W. SEYMOUR Monolithic electrode, related material, process for production, and use thereof

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