CN105047881A - Preparation method and application of germanium-carbon nitrogen nano composite material - Google Patents
Preparation method and application of germanium-carbon nitrogen nano composite material Download PDFInfo
- Publication number
- CN105047881A CN105047881A CN201510564252.1A CN201510564252A CN105047881A CN 105047881 A CN105047881 A CN 105047881A CN 201510564252 A CN201510564252 A CN 201510564252A CN 105047881 A CN105047881 A CN 105047881A
- Authority
- CN
- China
- Prior art keywords
- germanium
- carbon
- carbon nitrogen
- preparation
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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 germanium-carbon nitrogen nano composite material and a preparation method thereof. Firstly, germanium oxide nano wires are evenly dispersed in liquid-state organic ester, pyrrole, polyvinyl acetate and oxidative metal chlorine salt are added, and full stirring is performed for reaction so as to generate a germanium oxide-carbon nitrogen composite precursor; secondly, calcination is performed at the temperature of 600-1000 DEG C in the reducing atmosphere to obtain the germanium-carbon nitrogen nano composite electrode material; germanium nano particles in the prepared germanium-carbon nitrogen nano composite electrode material are mutually separated at intervals of certain distances and are injected into carbon nitrogen nano tubes in a sectioned mode to form a legume structure. The composite material prepared by means of the preparation method can be applied to lithium ion batteries, pores among discontinuous germanium particles in the material effectively buffer volume change occurred in the germanium charge-discharge process, meanwhile coating of a carbon nitrogen layer facilitates decrease of contact resistance and formation of a stable solid electrolyte interface, the electronic electric conductivity and electrochemical stability of electrodes are improved, and excellent lithium storage performance is shown.
Description
Technical field
The invention belongs to the preparation method and application field of lithium ion battery electrode material, more specifically, relate to preparation method and the application thereof of a kind of germanium-carbon nitrogen nano composite material.
Background technology
Lithium ion battery has the long-life due to it, energy density advantages of higher and be subject to extensive concern in power storage.Along with the rise of electric automobile and mobile electronic device, people have higher requirement for lithium ion battery energy-storage property.Performance of lithium ion battery is decided by electrode material, and the development of commercial li-ion positive electrode rapidly, from cobalt acid lithium, LiFePO4 to ternary material, become better and better, and commercial negative material is mainly based on material with carbon element by performance and fail safe.Specific capacity low (theoretical specific capacity is 372mAh/g), therefore, the silicon of exploitation high power capacity and germanium based combined electrode material are the important directions of lithium ion battery negative material development.
Advantages such as germanium, as lithium ion battery negative material, has capacity high (1600mAh/g), and the high and fail safe of conductivity is good and become the focus of research.Non-patent literature (HyojinLee, HansuKim, Seok-GwangDooandJaephilCho, SynthesisandOptimizationofNanoparticleGeConfinedinaCarbo nMatrixforLithiumBatteryAnodeMaterial, JournalofElectrochemicalSociety.2007,154 (4), A343-A346) germanium is modified upper organic group after annealing and obtain Ge/C mixture, capacity 1067mAh/g first, after 30 times, capacity keeps 88%.After carbon coated, cycle performance of battery is improved significantly, but or not ideal enough.
The coated nano material of carbon nitrogen pipe is due to its entirely coated architectural feature, electrolyte can be effectively stoped to contact with the direct of nano particle thus make its electrochemical interface more stable, thus cycle life and high rate performance also can be more outstanding, but in the prior art, usual use water is as solvent, utilize pyrroles as raw material Formed nitrogen pipe, as patent documentation CN201010601450 discloses a kind of tin dioxide-carbon nitrogen composite material and Synthesis and applications thereof, generate the carbon nitrogen pipe of coated tin dioxide nano-particle.But the solubility of germanium oxide in water is relatively large, the waste of material is not only easily caused after dissolving, also easily react in other material, be difficult to stablely generate germanium nano particle, therefore we need to find the preparation that new reaction system realizes germanium-carbon nitrogen nano composite material.
Summary of the invention
For above defect or the Improvement requirement of prior art, the present invention proposes a kind of germanium-carbon nitrogen nano composite material and preparation method thereof, its object is to the reaction system optimizing carbon-nitrogen nano tube, thus solve the problem that germanium oxide is easy to dissolving in traditional aqueous solvent.
For achieving the above object, according to one aspect of the present invention, provide the preparation method of a kind of germanium-carbon nitrogen nano composite material, it is characterized in that, comprise the following steps:
(1) germania nanoparticles line is dispersed in liquid organic ester, then pyrroles, oxidizability metal chloride and polyvinyl acetate is added wherein, stirring makes pyrroles fully be polymerized and wraps up described germania nanoparticles line, generates germanium oxide-carbon nitrogen composite precursor; Wherein, the weight proportion of each reactant is, in 100 parts, germania nanoparticles line, pyrroles is 5 parts ~ 15 parts, and oxidizability metal chloride is 30 parts ~ 70 parts, and polyvinyl acetate is 0 part ~ 15 parts;
(2) by germanium oxide-carbon nitrogen composite precursor 600 DEG C ~ 1000 DEG C calcinings in reducing atmosphere of gained in described step (1), the germanium-carbon nitrogen nano composite material of the coated germanium nano particle of carbon nitrogen pipe is obtained.
Preferably, the mixing time of step (1) is 6h ~ 30h.
Preferably, described liquid organic ester is methyl acetate or ethyl acetate.
Preferably, described oxidizability metal chloride is iron chloride, manganic chloride, manganese tetrachloride, butter of tin or germanium tetrachloride.
Preferably, the weight proportion of polyvinyl acetate is 5 parts ~ 10 parts.
Preferably, the calcination time of step (2) is 1h ~ 4h.
Preferably, described reducing atmosphere is by argon gas, and any one or two kinds of compositions in hydrogen and carbon monoxide, and wherein, the volume ratio of argon gas is 50vol.% ~ 96vol.%.
As further preferably, the volume ratio of argon gas is 70vol.% ~ 90vol.%.
According to another aspect of the present invention, additionally provide more than one and state germanium-carbon nitrogen nano composite material prepared by method, comprise germanium nano particle and carbon-nitrogen nano tube, mutually separate between multiple germanium nano particle, subsection filling is inner in carbon-nitrogen nano tube, and form pod-like structures, described germanium-carbon nitrogen nano composite material diameter is 20nm ~ 500nm, length-to-diameter is greater than 10, and carbon-nitrogen nano tube thickness is 2nm ~ 30nm.
According to another aspect of the present invention, additionally provide the application of a kind of above-mentioned nano composite material in lithium ion battery; Because carbon nitrogen pipe can stop electrolyte to contact with the direct of germanium nano particle, thus make its electrochemical interface more stable.
In general, the above technical scheme conceived by the present invention compared with prior art, by the selection to reaction dissolvent and reaction reagent, achieves following beneficial effect:
1, have selected as the solvent of reaction system, traditional aqueous solvent is replaced to the less organic ester of germanium oxide solubility, avoid germanium oxide dissolving and with other reagent generation side reaction, ensure that the successful preparation of germanium-carbon nitrogen nano composite material;
2, select can in organic ester uniform dissolution, and with the oxidizability metal chloride of other reagent generation side reaction as oxidant, the generation of pyrroles's polymerization reaction can not be ensure that;
3, utilize polyvinyl acetate as stabilizer, make reaction more even;
4, in the application of lithium ion battery, germanium-carbon nitrogen nano composite material is compared with traditional germanium-carbon nano-composite material, because carbon nitrogen pipe is a kind of half entirely coated hollow structure for germanium, electrolyte can be effectively stoped to contact with the direct of germanium, the space that germanium nano particle expands is provided simultaneously, thus make its electrochemical interface more stable, thus cycle life and high rate performance more outstanding;
The preparation cost of 5, germanium-carbon nitrogen nano composite material is low, and reaction condition temperature is closed, and step is simple, effectively can improve energy density and the power density of lithium ion battery, be expected to large-scale production.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction curve of germanium in embodiment 1-carbon nitrogen nano composite material;
Fig. 2 is the transmission electron microscope photo of germanium in embodiment 1-carbon nitrogen nano composite material;
Fig. 3 is the stereoscan photograph of germanium in embodiment 1-carbon nitrogen nano composite material;
Fig. 4 is that germanium in embodiment 1-carbon nitrogen nanocomposite applications is in the Electrochemical results of lithium ion battery.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.In addition, if below in described each execution mode of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
For achieving the above object, according to one aspect of the present invention, provide the preparation method of a kind of germanium-carbon nitrogen nano composite material, it is characterized in that, comprise the following steps:
(1) germania nanoparticles line is prepared
Prepare germania nanoparticles line presoma and often utilize following methods:
A, carbon thermal evaporation: fully grind after germanium dioxide powder is mixed with the mass ratio of 1:2 ~ 2:1 with active carbon, after be transferred to ceramic cap corundum boat, in Oxygen Flow, 700 DEG C ~ 950 DEG C insulation 2.5h ~ 4h, collect the germania nanoparticles line on ceramic cap.
B, altogether thermal evaporation: the iron powder mixing by HpGe powder and quality being 6% ~ 12% of germanium powder, at 120 DEG C ~ 180 DEG C, hot pressing is in blocks, and lower 750 DEG C ~ 950 DEG C insulation 1.5h ~ 3h of 150 Bristol ~ 200 Bristol pressure, collect germania nanoparticles line.
C, hydro thermal method: the germanium oxide and the water that particle diameter are less than 50nm mix with the mass ratio of 1:100 ~ 1:30, with autoclave sealing, at 400 DEG C ~ 500 DEG C, react 4h ~ 8h under 800rpm ~ 1200rpm speed of agitator, collect germania nanoparticles line at reactor inwall.
D, metal oxide assisting growth method: germanium dioxide powder and di-iron trioxide are ground with abundant after the mixing of the mass ratio of 8:1 ~ 15:1, joining quality is in the mixed solution of 3 times ~ water doubly of germanium dioxide and the ethylenediamine of 2 times ~ 4 times, at the Water Under thermal response 60h ~ 90h of 150 DEG C ~ 230 DEG C, suspended matter is taken out after being cooled to room temperature, three times are cleaned respectively with ethanol and water, product is put into 400 DEG C ~ 700 DEG C calcining 1h ~ 3h in air, obtains germania nanoparticles line.
(2) be that the germania nanoparticles line of 100 parts is dispersed in liquid organic ester solvent by weight, add the pyrroles of 5 parts ~ 15 parts, oxidizability metal chloride (parts by weight proportioning) that the polyvinyl acetate of 0 part ~ 15 parts and 30 parts ~ 70 parts have oxidizability, stirring makes oxidizability metal chloride and pyrroles fully react, pyrroles be polymerized and be wrapped in germania nanoparticles line surrounding, generating germanium oxide-carbon nitrogen composite precursor; Its reaction time is relevant with the concentration of the amount of substance and reactant that participate in reaction, is preferably 6h ~ 30h, more preferably 15h ~ 20h.
Wherein, liquid organic ester solvent can not react with each reactant on the one hand, and need there is less solubility to germanium oxide on the other hand, in order to avoid germanium oxide generation side reaction, liquid organic ester is preferably methyl acetate or ethyl acetate.
Polyvinyl acetate in the reaction as stabilizer, reaction can be made to occur more even, its parts by weight are preferably 5 parts ~ 10 parts.
Pyrroles is as the precursor of carbon-nitrogen nano tube, and its weight proportion is preferably 8 parts ~ 12 parts.
Oxidant is used for that oxidizable pyrrole is polymerized and generates polypyrrole, because the oxidant that can dissolve in organic ester is very limited, so have selected oxidizability metal chloride in this reaction system, as iron chloride, manganic chloride, manganese tetrachloride, butter of tin or germanium tetrachloride, consider from production cost, more preferably iron chloride; The addition of oxidant is relevant to its molecular weight, generally speaking says that its weight proportion is preferably 40 parts ~ 60 parts;
(3) by after the germanium oxide-carbon nitrogen composite precursor filtration washing of gained in (2), 600 DEG C ~ 1000 DEG C calcinings in reducing atmosphere, obtain germanium-carbon nitrogen nano composite material; In calcination process, germanium oxide is reduced to germanium nano particle on the one hand, on the other hand polypyrrole carbonization Formed nitride nanotubes; This reaction temperature is preferably 650 DEG C ~ 800 DEG C, reaction time is relevant with the amount of substance participating in reaction, it is incomplete that reaction time crosses short reaction, and long meeting causes the sintering of material, liquid germanium also may melt out from pipe, affect pattern, therefore the reaction time is preferably 1h ~ 4h, more preferably 2h ~ 3h.
Reducing atmosphere uses the mist of inert gas and hydrogen or carbon monoxide aborning usually, the reducing atmosphere that the present invention adopts is the mist of hydrogen and argon gas, carbon monoxide and argon gas mist, or the mist of hydrogen, carbon monoxide and argon gas, wherein the cumulative volume of hydrogen and carbon monoxide is than being preferably 4% ~ 50%, and more preferably 10% ~ 30%.
The germanium prepared according to above step-carbon nitrogen nano composite material comprises germanium nano particle and carbon-nitrogen nano tube, germanium nano particle is separated at a certain distance mutually, subsection filling is inner in carbon-nitrogen nano tube, form pod-like structures, described composite material diameter is 20nm ~ 500nm, length-to-diameter is more than or equal to 10, and carbon-nitrogen nano tube thickness is 2nm ~ 30nm.
According to another aspect of the present invention, additionally provide the application of a kind of above-mentioned electrode material in lithium ion battery.Due to pod-like structures germanium-carbon nitrogen nano composite material due to its inside be discontinuous germanium nano particle, provide change in volume space large in germanium charge and discharge process, the carbon-nitrogen nano tube structure on surface simultaneously, provide electron propagation ducts, also be conducive to forming stable solid electrolyte interface structure, effectively can solve Problems existing in the application of germanium nano-electrode material, obtain the germanium based combined electrode material with excellent cycling stability and high rate performance.
Embodiment 1
(1) 2g germanium oxide and 0.5g active carbon agate mortar are ground 5min until mix, this mixture is transferred in the water heating kettle of 100ml, 12ml water and 8ml ethylenediamine is added in water heating kettle, water heating kettle is sealed, put into 200 DEG C of baking oven insulation 96h, treat that water heating kettle is cooled to room temperature, take out the suspended matter of white in above-mentioned solution, wash three times with distilled water and ethanol.Product is put into Muffle furnace 500 DEG C of air calcination 2h.
(2) product got after 200mg calcining evenly spreads in 20ml anhydrous acetic acid methyl esters, adds the anhydrous ferric trichloride of 20mg polyvinyl acetate and 100mg, stirs and make it form uniform dispersion.Then in dispersion liquid, 20 microlitre pyrroles are dripped, stirring at room temperature 24h.Products therefrom filtering and washing three times, at 50 DEG C of temperature, 5h is dried.
(3) by products therefrom in containing 10% hydrogen argon hydrogen gaseous mixture in 700 DEG C calcining 2h, heating rate 15 DEG C/min, obtain germanium-carbon nitrogen nanometer combined electrode material.
Product X x ray diffraction (XRD) curve as shown in Figure 1, can see the diffraction maximum of germanium, carbon and nitrogen, proves that the material prepared is really containing germanium nano particle and carbon nitrogen pipe.
Product transmission electron microscope as shown in Figure 2, can be seen, germanium nano particle is separated at a certain distance mutually, and subsection filling is inner in carbon-nitrogen nano tube, forms pod-like structures.Utilize scanning electron microscopic observation product, a large amount of germanium-carbon nitrogen nano composite material can be seen, confirm that the method has the high production efficiency of effect, as shown in Figure 3 a, and the longest submillimeter level that reaches of material, as shown in Figure 3 b.
2025 type button cells are adopted to test its chemical property.Fig. 4 is the rate charge-discharge result resolution chart of material, and as can be seen from the figure, along with current density increases, its capacity suppression ratio is comparatively slow, and illustrative material has good high rate performance.And circulation volume maintenance is several times stable under each multiplying power, when current density returns low range, the recovery that capacity can be good, demonstrates this material and has good cyclical stability.
Embodiment 2
(1) 1.5g germanium dioxide powder and 1.5g active carbon are fully ground, after be transferred to ceramic cap corundum boat, in Oxygen Flow size 20sccm, 840 DEG C of insulation 3.5h, collect the germanium oxide presoma on ceramic cap.
(2) get 300mg presoma to evenly spread in 20ml anhydrous acetic acid methyl esters, add the anhydrous ferric trichloride of 15mg polyvinyl acetate and 90mg, stir and make it form uniform dispersion.Then in dispersion liquid, 15mg pyrroles is dripped, stirring at room temperature 30h.Products therefrom filtering and washing three times, dries 5h in 50 DEG C.
(3) by products therefrom in containing 4% hydrogen argon hydrogen gaseous mixture in 650 DEG C calcining 4h, heating rate 1 DEG C/min.Obtain germanium-carbon nitrogen nanometer combined electrode material, electro-chemical test part is with embodiment 1, and prepared material presents the experimental result almost identical with embodiment 1.
Embodiment 3
(1) mixed by the iron powder of HpGe powder and 8% quality, at 150 DEG C, hot pressing is in blocks, and the lower 820 DEG C of insulation 2h of 200 Bristol pressure, collect germanium oxide presoma at quartz ampoule inwall.
(2) get 300mg presoma to evenly spread in 20ml anhydrous acetic acid methyl esters, add the anhydrous ferric trichloride of 45mg polyvinyl acetate and 210mg, stir and make it form uniform dispersion.Then in dispersion liquid, 45mg pyrroles is dripped, stirring at room temperature 12h.Products therefrom filtering and washing three times, dries 5h in 50 DEG C.
(3) by products therefrom in containing 15% carbon monoxide argon/carbon mono oxide mixture in 1000 DEG C calcining 1h, heating rate 5 DEG C/min.Obtain germanium-carbon nitrogen nanometer combined electrode material.Electro-chemical test part is as embodiment 1, and resulting materials presents the chemical property almost identical with embodiment 1.
Embodiment 4
(1) by 2g germanium oxide and 0.5gFe
2o
3with agate mortar grinding 5min until mix, this mixture is transferred in the water heating kettle of 100ml, 12ml water and 8ml ethylenediamine is added in water heating kettle, water heating kettle is sealed, put into 200 DEG C of baking oven insulation 96h, treat that water heating kettle is cooled to room temperature, take out the suspended matter of white in above-mentioned solution, wash three times with distilled water and ethanol.Product is put into Muffle furnace 500 DEG C of air calcination 2h.
(2) product got after 200mg calcining evenly spreads in 20ml anhydrous acetic acid methyl esters, adds the anhydrous ferric trichloride of 20mg polyvinyl acetate and 80mg, stirs and make it form uniform dispersion.Then in dispersion liquid, 16 microlitre pyrroles are dripped, stirring at room temperature 24h.Products therefrom filtering and washing three times, dries 5h in 50 DEG C.
(3) by products therefrom in containing 30% hydrogen argon hydrogen gaseous mixture in 700 DEG C calcining 2h, heating rate 15 DEG C/min, obtain germanium-carbon nitrogen nanometer combined electrode material, electro-chemical test part is with embodiment 1, and prepared material presents the experimental result almost identical with embodiment 1.
Embodiment 5
(1) by 2g germanium oxide and 0.5gFe
2o
3with agate mortar grinding 5min until mix, this mixture is transferred in the water heating kettle of 100ml, 12ml water and 8ml ethylenediamine is added in water heating kettle, water heating kettle is sealed, put into 200 DEG C of baking oven insulation 96h, treat that water heating kettle is cooled to room temperature, take out the suspended matter of white in above-mentioned solution, wash three times with distilled water and ethanol.Product is put into Muffle furnace 500 DEG C of air calcination 2h.
(2) product got after 200mg calcining evenly spreads in 20ml anhydrous acetic acid methyl esters, adds the anhydrous ferric trichloride of 20mg polyvinyl acetate and 120mg, stirs and make it form uniform dispersion.Then in dispersion liquid, 24 microlitre pyrroles are dripped, stirring at room temperature 24h.Products therefrom filtering and washing three times, dries 5h in 50 DEG C.
(3) by products therefrom in containing the hydrogen of 25%, the carbon monoxide of 25% and 50% argon gas mist in 600 DEG C calcining 3h, heating rate 15 DEG C/min, obtain germanium-carbon nitrogen nanometer combined electrode material.Electro-chemical test part is with embodiment 1, and prepared material presents the experimental result almost identical with embodiment 1.
Embodiment 6
(1) by 2g germanium oxide and 0.5gFe
2o
3with agate mortar grinding 5min until mix, this mixture is transferred in the water heating kettle of 100ml, 12ml water and 8ml ethylenediamine is added in water heating kettle, water heating kettle is sealed, put into 200 DEG C of baking oven insulation 96h, treat that water heating kettle is cooled to room temperature, take out the suspended matter of white in above-mentioned solution, wash three times with distilled water and ethanol.Product is put into Muffle furnace 500 DEG C of air calcination 2h.
(2) product got after 200mg calcining evenly spreads in 20ml anhydrous acetic acid methyl esters, adds the anhydrous ferric trichloride of 20mg polyvinyl acetate and 100mg, stirs and make it form uniform dispersion.Then in dispersion liquid, 20 microlitre pyrroles are dripped, stirring at room temperature 24h.Products therefrom filtering and washing three times, dries 5h in 50 DEG C.
(3) by products therefrom in containing 10% carbon monoxide argon/carbon mono oxide mixture in 800 DEG C calcining 2.5h, heating rate 15 DEG C/min, obtain germanium-carbon nitrogen nanometer combined electrode material.Electro-chemical test part is with embodiment 1, and prepared material presents the experimental result almost identical with embodiment 1.
Embodiment 7
Repeat embodiment 1 with described same steps, difference is, the mixing time of step (2) is 6h, and the volume of pyrroles is 14 microlitres, and prepared material presents the experimental result almost identical with embodiment 1.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for germanium-carbon nitrogen nano composite material, is characterized in that, comprise the following steps:
(1) germania nanoparticles line is dispersed in liquid organic ester, then adds pyrroles, oxidizability metal chloride and polyvinyl acetate wherein, stir fully reaction and generate germanium oxide-carbon nitrogen composite precursor; Wherein, the weight proportion of each reactant is, in 100 parts, germania nanoparticles line, pyrroles is 5 parts ~ 15 parts, and oxidizability metal chloride is 30 parts ~ 70 parts, and polyvinyl acetate is 0 part ~ 15 parts;
(2) by germanium oxide-carbon nitrogen composite precursor 600 DEG C ~ 1000 DEG C calcinings in reducing atmosphere of gained in described step (1), germania nanoparticles line is made to be reduced to germanium nano particle, and polypyrrole carbonization becomes carbon-nitrogen nano tube, obtain the germanium-carbon nitrogen nano composite material of the coated germanium nano particle of carbon nitrogen pipe.
2. preparation method as claimed in claim 1, it is characterized in that, the mixing time of step (1) is 6h ~ 30h.
3. preparation method as claimed in claim 1, it is characterized in that, described liquid organic ester is methyl acetate or ethyl acetate.
4. preparation method as claimed in claim 1, it is characterized in that, described oxidizability metal chloride is iron chloride, manganic chloride, manganese tetrachloride, butter of tin or germanium tetrachloride.
5. preparation method as claimed in claim 1, it is characterized in that, the weight proportion of polyvinyl acetate is 5 parts ~ 10 parts.
6. preparation method as claimed in claim 1, it is characterized in that, the calcination time of described step (2) is 1h ~ 4h.
7. preparation method as claimed in claim 1, is characterized in that, described reducing atmosphere is by argon gas, and any one or two kinds of compositions in hydrogen and carbon monoxide, and wherein, the volume ratio of argon gas is 50vol.% ~ 96vol.%.
8. preparation method as claimed in claim 7, it is characterized in that, the volume ratio of argon gas is 70vol.% ~ 90vol.%.
9. the germanium prepared with method described in any one in claim 1-8-carbon nitrogen nano composite material, comprise germanium nano particle and carbon-nitrogen nano tube, it is characterized in that, mutually separate between multiple germanium nano particle, subsection filling is inner in carbon-nitrogen nano tube, and form pod-like structures, described germanium-carbon nitrogen nano composite material diameter is 20nm ~ 500nm, length-to-diameter is greater than 10, and carbon-nitrogen nano tube thickness is 2nm ~ 30nm.
10. the application of nano composite material in lithium ion battery as claimed in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510564252.1A CN105047881B (en) | 2015-09-06 | 2015-09-06 | Preparation method and application of germanium-carbon nitrogen nano composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510564252.1A CN105047881B (en) | 2015-09-06 | 2015-09-06 | Preparation method and application of germanium-carbon nitrogen nano composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105047881A true CN105047881A (en) | 2015-11-11 |
| CN105047881B CN105047881B (en) | 2017-04-12 |
Family
ID=54454260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510564252.1A Expired - Fee Related CN105047881B (en) | 2015-09-06 | 2015-09-06 | Preparation method and application of germanium-carbon nitrogen nano composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105047881B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106169572A (en) * | 2016-09-18 | 2016-11-30 | 复旦大学 | A kind of N doping cladding germanium composite lithium ion battery negative material and its preparation method and application |
| CN108281627A (en) * | 2018-01-03 | 2018-07-13 | 中国科学院上海硅酸盐研究所 | A kind of lithium ion battery germanium carbon compound cathode materials and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8642432B2 (en) * | 2011-12-01 | 2014-02-04 | International Business Machines Corporation | N-dopant for carbon nanotubes and graphene |
| CN103454327B (en) * | 2013-09-06 | 2016-01-20 | 南京理工大学 | P3MT/N-GE modified glassy carbon electrode and the application in detection pesticide phoxim |
| CN104659346A (en) * | 2015-02-11 | 2015-05-27 | 深圳新宙邦科技股份有限公司 | Germanium/carbon composite negative electrode material and preparation method thereof |
-
2015
- 2015-09-06 CN CN201510564252.1A patent/CN105047881B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106169572A (en) * | 2016-09-18 | 2016-11-30 | 复旦大学 | A kind of N doping cladding germanium composite lithium ion battery negative material and its preparation method and application |
| CN108281627A (en) * | 2018-01-03 | 2018-07-13 | 中国科学院上海硅酸盐研究所 | A kind of lithium ion battery germanium carbon compound cathode materials and preparation method thereof |
| CN108281627B (en) * | 2018-01-03 | 2021-05-25 | 中国科学院上海硅酸盐研究所 | Germanium-carbon composite negative electrode material for lithium ion battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105047881B (en) | 2017-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Zn-ion hybrid supercapacitors: achievements, challenges and future perspectives | |
| Yi et al. | Ionic liquid-assisted synthesis of nickel cobalt phosphide embedded in N, P codoped-carbon with hollow and folded structures for efficient hydrogen evolution reaction and supercapacitor | |
| Bi et al. | One-pot microwave synthesis of NiO/MnO2 composite as a high-performance electrode material for supercapacitors | |
| CN102299326B (en) | Graphene modified lithium iron phosphate/carbon composite material and its application | |
| CN103346303B (en) | A kind of Si-C composite material and preparation method thereof, lithium ion battery | |
| CN103208625B (en) | Preparation method of ferroferric-oxide-based high-performance negative electrode material for lithium ion battery | |
| CN104538200A (en) | Graphene / Fe-MOFs composite material and preparation method thereof | |
| CN103682274A (en) | Graphene/polyaniline/sulfur composite material and preparation method thereof | |
| Zhang et al. | A fast and stable sodium-based dual-ion battery achieved by Cu3P@ P-doped carbon matrix anode | |
| CN102842710A (en) | Preparation method of Co3O4/graphene nanocomposite material | |
| CN104176783B (en) | The preparations and applicatio method of the coated manganese dioxide nanowire of a kind of nitrogen carbon material | |
| CN107768617B (en) | Lithium-sulfur battery composite cathode material and preparation method thereof | |
| CN106158405A (en) | A kind of nickel hydroxide/graphene nanocomposite material and preparation method thereof, electrode of super capacitor and ultracapacitor | |
| CN110838583B (en) | Carbon nanotube/M-phase vanadium dioxide composite structure, preparation method thereof and application thereof in water-based zinc ion battery | |
| CN105406042A (en) | Preparation method for carbon-coated super-long titanium dioxide nanotube negative electrode material of lithium ion battery | |
| Duan et al. | MOF-71 derived layered Co-CoP/C for advanced Li-S batteries | |
| CN104600271A (en) | Preparation method of sodium titanate/graphene composite cathode material of sodium ion battery | |
| Zhang et al. | A novel SnS2 nanomaterial based on nitrogen-doped cubic-like carbon skeleton with excellent lithium storage | |
| CN105244503A (en) | Method for preparing graphene-grading-modification spherical sodium-ion battery electrode material | |
| CN103606700A (en) | Lithium ion battery with good charge and discharge performance | |
| Song et al. | Effect of heteroatom doping on the charge storage and operating voltage window of nickel-based sulfide composite electrodes in alkaline electrolytes | |
| Zhao et al. | Nondestructive CNT chained Fe3O4 anode materials for high-performance Li-ion batteries | |
| Mao et al. | Advanced Aqueous Zinc‐Ion Batteries Enabled by 3D Ternary MnO/Reduced Graphene Oxide/Multiwall Carbon Nanotube Hybrids | |
| CN105514374A (en) | Graphitized carbon coated manganese-fluorine oxide material and preparation method thereof | |
| CN105047881A (en) | Preparation method and application of germanium-carbon nitrogen nano composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170412 Termination date: 20180906 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |