CN105977483A - Carbon-based nanocomposite material for electrode - Google Patents

Carbon-based nanocomposite material for electrode Download PDF

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CN105977483A
CN105977483A CN201610326177.XA CN201610326177A CN105977483A CN 105977483 A CN105977483 A CN 105977483A CN 201610326177 A CN201610326177 A CN 201610326177A CN 105977483 A CN105977483 A CN 105977483A
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carbon
asp
electrode
based nano
nano composite
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范黎黎
康子曦
王荣明
孙道峰
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China University of Petroleum East China
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China University of Petroleum East China
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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
    • H01M4/48—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
    • 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
    • H01M4/36—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
    • H01M4/58—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a carbon-based nanocomposite material for an electrode, and belongs to the field of preparation of metal@carbon nanocomposite materials. According to a preparation method, the carbon-based nanocomposite material for the electrode is obtained by high-temperature pyrolysis of a metal-organic skeleton compound in an inert protective atmosphere. The metal-organic skeleton compound [Ni2(L-asp)2(bpy)] is utilized as a precursor; and the carbon-based nanocomposite material with a uniform dimension is prepared through a one-step high-temperature pyrolysis process. The product obtained by the method is single in phase, very few in impurities, especially easy to collect, high in yield and beneficial to large-scale synthesis; and the microstructure of the carbon-based nanocomposite material prepared by the method has excellent properties of high stability and the like in application of the electrode material of a lithium-ion battery.

Description

A kind of carbon-based nano composite for electrode
Technical field
The invention belongs to metal@carbon nano-composite material preparation field, be specifically related to a kind of carbon-based nano composite wood for electrode Material.
Background technology
Non-renewable resources day by day exhausted makes the development and utilization of new forms of energy extremely urgent.With tide energy, wind energy, solar energy New forms of energy for representing have bigger randomness with intermittent in power output, in order to realize grid-connected application, energy storage with Transformation technology, especially the chemical energy storage technology with secondary cell system as representative are of increased attention.Wherein, may be used Rechargeable lithium ion battery because of have have extended cycle life, the advantage such as self discharge is low, running voltage is high, specific energy is high, memory-less effect, Dominate secondary cell market it is considered to be the most promising energy storage system in future.The Chinese government goes out the most successively Platform major policy measure is supported and development New Energy Industry, it is desirable at the energy density of lithium ion battery, high power discharge and whole The aspects such as body safety obtain important breakthrough.
The charge/discharge mechanism of lithium ion battery is based on " rocking chair " concept.During charging, lithium ion departs from from positive electrode, thoroughly Cross barrier film and move to negative pole, embed and be stored in negative material after negative pole one electronics of capture is reduced to lithium.During electric discharge, Lithium in negative pole loses an electronics and becomes lithium ion, migrates through barrier film to positive extreme direction and is stored in positive electrode.Filling During electricity/electric discharge, chemical energy is changed into electric energy and stores in the battery.The performance of lithium ion battery depends on to a great extent In positive electrode and negative material.At present, the positive electrode of commercialization is existing several, and business-like negative material is then the most single One, mainly native graphite and material modified.Its cheap cost and security performance are to promote its leading commercial Li-ion electricity The key factor of pond negative material.But, graphite theoretical specific capacity is relatively low, and high rate performance is not good enough, constrains lithium ion battery Development further.Therefore, increasing researcher starts to research and develop novel negative material.
In recent years, the chemical property of nano material is furtherd investigate, compared to commercial micronsize material, nano material Having the most excellent battery performance, the increase of surface area can promote the interaction between electrolyte and electrode, reduces internal Resistance, increases energy density.But, nano material also has a weak point, and such as in charge/discharge process, the change of volume is relatively Greatly, interparticle reunion can be caused, cause the reduction of material circulation capacity.And the mechanical stress induced may result in electrode material Quickly disintegrating of material.Meanwhile, nano material also can increase the probability forming thicker solid electrolyte interface film, and thicker SEI Film can consume part lithium.Therefore, single-phase Application of micron is that battery electrode material has certain limitation.If will receive Rice material dispersion or be coated on that there is resiliency and can keep among the substrate of electric property of particle, it is possible to be obviously improved These are not enough.And material with carbon element is exactly one of ideal candidate as buffer matrix, if the nano material of electro-chemical activity will be had Combine with the material with carbon element of high conductivity and prepare carbon-based nano composite, charge migration speed and lithium ion can be significantly improved Diffusion rate, and alleviate the Volumetric expansion in charge and discharge process to a certain extent, thus realize longer cycle life with Excellent high rate during charging-discharging.
Generally the preparation method of carbon-based nano composite have blending method, in-situ synthesis, template, vacuum vapor deposition, Sputtering method, chemical vapour deposition technique, sol-gal process, electrochemical deposition method and self-assembly method etc..Here, in order to make For going out high performance ion cathode material lithium and accomplishing scale production, we use a kind of novel and simple preparation method: with Metal-organic framework materials is presoma, is pyrolyzed carbonization through a step and obtains high uniformity scattered carbon-based nano composite.Gold Genus-organic framework material is that inorganic metal ion has periodic network structure with organic ligand by what self assembling process was constructed Inorganic-organic hybridization porous material.Such material has structured designability and Modulatory character, is combined as preparing carbon-based nano The persursor material of material mainly has a following advantage:
One, metal center has multiformity, can screen according to application demand, selects space big；
Two, during high temperature, organic ligand is carbonized formation carbon-coating and is coated on metal center surface, and metal center is then in the reduction of carbon It is reduced generation metal nanoparticle under property effect, the reunion of nano-particle can be prevented effectively from, keep the most equal Even property, and preparation process need not additionally introduce source metal or carbon source；
Three, the synthesis condition of major part MOFs material is the gentleest, and some even can synthesize under room temperature condition of normal pressure, There are the potentiality accomplished scale production.
Four, the method operating flexibility is high, requires relatively low to conditions such as equipment, and simple to operate, only by a step The most available preferable carbon-based nano composite of reaction.Compared to additive method, this method is simple and controlled Property strong, be new method preferable, potential.
We utilize the method, select as requested required metal ion as the metal center of metal-organic framework compound, The carbon-based material with certain microstructure is generated by a step pyrolytic process catalysis, for lithium ion battery negative material after synthesis.
Summary of the invention
It is an object of the invention to provide a kind of by means of metal-organic framework compound [Ni2(L-asp)2(bpy)] a kind of lithium is prepared The method of the carbon-based nano composite of ion battery cathode material.
In the present invention, technical problem to be solved is achieved by the following technical programs:
A kind of carbon-based nano composite for electrode, described carbon-based nano composite is that employing includes metal-organic framework Compound, under inert protective atmosphere, high temperature pyrolysis obtains.
Further, the compound of described metal-organic framework is, the two-dimensional layer chemical combination that metallic compound and Organic substance are formed Thing, and the three dimensional skeletal structure built by the pillared effect of organic ligand.
Further, described metal-organic framework compound is [Ni2(L-asp)2(bpy)]·CH3OH·H2O, is by basic carbonate The two-dimensional layer compound that nickel and aspartic acid L-asp are formed connects, by organic ligand 4,4'-, the three-dimensional that the pillared effect of pyridine is built Framing structure.
Further, the duct size of described three dimensional skeletal structure is
Further, described preparation method comprises the following steps:
(1)Ni(L-asp)(H2O)2Preparation: by NiCO3·2Ni(OH)2·xH2O, L-asp and H2O 1:(0.5 in mass ratio～3): (100～500) mix, and heated and stirred 0.5～5 hours under the conditions of being maintained at 60～100 DEG C, to major part powder soluble in water after Stop heating and stirring；Filtration removes the insoluble matter in solution and obtains settled solution, and puts into standing in 60～120 DEG C of baking ovens 0.5～2 day, after aqueous solvent volatilization completely, i.e. obtain green Ni (L-asp) (H2O)2Crystal；
(2)[Ni2(L-asp)2(bpy)] the preparation of crystalline material: Ni (the L-asp) (H that step (1) is obtained2O)2Join methanol With in the mixed solution of water, continuing to add 4 under agitation after being partly dissolved, 4'-connects pyridine so that each material in final solution Mass ratio be Ni (L-asp) (H2O)2: 4,4'-connects pyridine: methanol: water=1:0.5～10:1～80:1～80；This solution is turned Move to autoclave seals, crystallization 1～4 days in 80～180 DEG C of baking ovens；After question response still is cooled to room temperature, by filtering, Wash and be dried to obtain aeruginous [Ni2(L-asp)2(bpy)] crystal powder；
(3) preparation of carbon-based nano the composite: [Ni that step (2) is synthesized2(L-asp)2(bpy)] crystal powder is ground to Exist without larger particles and be laid in bottom ceramic crucible, this porcelain crucible being placed in the middle part of tube furnace, is then removed by evacuation The inner air of tube furnace, replaces with high pure nitrogen, repeat 2～5 times to ensure sufficient oxygen-free environment, at 600～1200 DEG C Under the conditions of be pyrolyzed after 2～8 hours, obtain metal@carbon composite；After concentrated hydrochloric acid processes 1～5 day, it is washed with deionized water Wash 3～6 times, separate and obtain the carbon-based nano composite for electrode after drying.
Further, being used temperature programming by room temperature to pyrolysis temperature in described step (3), programming rate is 2～10 DEG C per second.
Further, [Ni in described step (3) temperature-rise period2(L-asp)2(bpy)] crystal powder in temperature-rise period at 100～200 DEG C Stop 0.5～4 hour, with the solvent molecule remained in removing plane of crystal and duct.
Further, the flow velocity of nitrogen is controlled by suspended body flowmeter, and flow velocity is per minute 20～120ml.
Further, described concentrated hydrochloric acid processing mode is to be dipped in completely among concentrated hydrochloric acid by powder body material.
Further, the carbon-based nano composite for electrode that prepared by described method is in the application of lithium ion battery electrode material.
Beneficial effects of the present invention is as follows:
The present invention is by utilizing metal-organic framework compound [Ni2(L-asp)2(bpy)] it is predecessor, by a step high temperature pyrolysis mistake Journey prepares the carbon-based nano composite of size uniform.The product that the method obtains is mutually single, and impurity is few, is especially susceptible to receive Collection, and yield is high, is conducive to extensive synthesis.The carbon-based nano composite prepared by the method, its microstructure exists There is in the application of lithium ion battery electrode material the superior functions such as stability is high.
Accompanying drawing explanation
Fig. 1 (a): [Ni2(L-asp)2(bpy)] crystal structure simulation X-ray diffraction spectrogram.
[the Ni of synthesis in Fig. 1 (b): embodiment 12(L-asp)2(bpy)] the X-ray diffraction spectrogram of crystal powder.
[the Ni of synthesis in Fig. 2: embodiment 12(L-asp)2(bpy)] the thermogravimetric curve of crystal powder.
The transmission electron micrograph of the carbon-based nano composite for electrode prepared in Fig. 3 (a): embodiment 1.
The transmission electron micrograph of the carbon-based nano composite for electrode prepared in Fig. 3 (b): embodiment 2.
The transmission electron micrograph of the carbon-based nano composite for electrode prepared in Fig. 3 (c): embodiment 3.
The transmission electron micrograph of the carbon-based nano composite for electrode prepared in Fig. 3 (d): embodiment 6.
The carbon-based nano composite for electrode prepared in Fig. 4: embodiment 1 is at electric current 100mA g-1Under the conditions of record Charge-discharge curves.
The carbon-based nano composite for electrode prepared in Fig. 5: embodiment 2 is at electric current 100mA g-1Under the conditions of survey The charge-discharge curves obtained.
The carbon-based nano composite for electrode prepared in Fig. 6: embodiment 3 is at electric current 100mA g-1Under the conditions of survey The charge-discharge curves obtained.
The carbon-based nano composite for electrode prepared in Fig. 7: embodiment 4 survey under the conditions of electric current 100mA g-1 The charge-discharge curves obtained.
The carbon-based nano composite for electrode prepared in Fig. 8: embodiment 5 survey under the conditions of electric current 100mA g-1 The charge-discharge curves obtained.
The carbon-based nano composite for electrode prepared in Fig. 9: embodiment 6 is at electric current 100mA g-1Under the conditions of survey The charge-discharge curves obtained.
Detailed description of the invention
Being embodied as the following detailed description of the present invention, it is necessary to it is pointed out here that, below implement to be only intended to entering of the present invention One step explanation, it is impossible to be interpreted as the restriction to invention protection domain, this art skilled person is according to the invention described above content pair Some nonessential improvement and adjustment that the present invention makes, still fall within protection scope of the present invention.
The relevant testing conditions that the present invention relates to and method:
X-ray diffraction (XRD): XRD test uses the Ultima IV type diffractometer of Rigaku company.Use Cu-KaLaunching site, fixed power source is 40kV and 30mA, and scanning 2theta scope is 4～40 °.
Thermogravimetric analysis (TGA): thermogravimetric curve is tested on Jupiter STA449 F3 type thermogravimetric analyzer, uses nitrogen Gas atmosphere, flow velocity is 30ml/min.
Transmission electron microscope (SEM): SEM test uses FEI Co.'s Tecnai F20 type transmission electron microscope. Accelerating potential is 200kV.
Lithium electric performance test: the lithium electrical property of nano material is CR 2032 coin-cell and the LAND battery testing by standard System characterizes.
Embodiment 1:
(1)Ni(L-asp)(H2O)2Preparation: by NiCO3·2Ni(OH)2·xH2O, L-asp and H2O 1:1:200 in proportion Mixing, and heated and stirred 2.5 hours under the conditions of being maintained at 95 DEG C, to major part powder soluble in water after stop heating and stirring. Filtration removes the insoluble matter in solution and obtains settled solution, and puts into standing 1 day in 100 DEG C of baking ovens, treats that aqueous solvent is volatilized Green Ni (L-asp) (H is i.e. obtained after Wan Quan2O)2Crystal, collects standby.
(2)[Ni2(L-asp)2(bpy)] the preparation of crystalline material: Ni (the L-asp) (H that will prepare in previous step2O)2Join first In the mixed solution of alcohol and water, continuing to add a certain amount of 4 under agitation after being partly dissolved, 4'-connects pyridine so that the most molten In liquid, the mass ratio of each material is Ni (L-asp) (H2O)2: 4,4'-connects pyridine: methanol: water=1:4:21.7:27.4.Should Solution is transferred in autoclave seal, crystallization 2 days in 150 DEG C of baking ovens.After question response still is cooled to room temperature, by mistake Filter, wash and be dried etc. operates and obtains aeruginous [Ni2(L-asp)2(bpy)] crystal powder.
(3) preparation method of magnetic the Carbon en capsulated nanomaterials: [Ni that will synthesize2(L-asp)2(bpy)] crystal powder be lightly ground to Exist without larger particles and be laid in bottom ceramic crucible, this porcelain crucible being placed in the middle part of tube furnace, is then removed by evacuation The inner air of tube furnace, replaces with high pure nitrogen, is repeated 3 times to ensure sufficient oxygen-free environment, the flow velocity control of nitrogen System is at 80ml per minute, and programming rate is 5 DEG C per second, first stops 2 hours at 150 DEG C, after under the conditions of 1000 DEG C, be pyrolyzed 5 Hour, obtain metal@carbon composite.
(4) the metal@carbon composite obtained is immersed in concentrated hydrochloric acid, disperse 5min under Ultrasonic Conditions, stand 2 days, adopt By centrifugal separation and be washed with deionized 5 times, after drying, obtain the final carbon-based nano composite for electrode.
(5) preparation of combination electrode is by carbon-based nano composite, binding agent and the acetylene black 8:1:1 in mass ratio of synthesis Mixing, and it is evenly applied to copper foil surface, dry 12 hours in 60 DEG C of baking ovens.By tablet machine, combination electrode is pressed into 12mm The disk of diameter, and at glove box (MBRAUN Unilab, O2<0.1ppm,H2O < 0.1ppm) in be assembled under the conditions of argon Lithium ion battery.Between positive pole negative pole by Celgard macromolecule membrane separately, LiPF will be contained6Concentration is the carbonic acid of 1mol/L The mixture of vinyl acetate, dimethyl carbonate and diethyl carbonate 1:1:1 by volume mixing is as electrolyte.
(6) sign of material: to [Ni2(L-asp)2(bpy)] crystal powder carries out X-ray diffraction and thermogravimetric analysis characterizes, to carbon back Nano composite material carries out transmission electron microscope and characterizes and performance of lithium ion battery sign.
Embodiment 2:
[Ni is prepared by step (1) and (2) in embodiment 12(L-asp)2(bpy)] crystal powder material.
[the Ni that will synthesize2(L-asp)2(bpy)] crystal powder is lightly ground to existing without larger particles and being laid at the bottom of ceramic crucible Portion, is placed in the middle part of tube furnace by this porcelain crucible, is then removed the inner air of tube furnace by evacuation, carries out with high pure nitrogen Displacement, is repeated 3 times to ensure sufficient oxygen-free environment, the flow speed control of nitrogen is at 80ml per minute, and programming rate is 5 DEG C per second, First stop 2 hours at 150 DEG C, after be pyrolyzed 5 hours under the conditions of 900 DEG C, obtain metal@carbon composite.
Repeat step (4) and step (5) in embodiment 1, and the carbon-based nano composite for electrode is carried out transmitted electron Microscope characterizes and performance of lithium ion battery characterizes.
Embodiment 3:
[Ni is prepared by step (1) and (2) in embodiment 12(L-asp)2(bpy)] crystal powder material.
[the Ni that will synthesize2(L-asp)2(bpy)] crystal powder is lightly ground to existing without larger particles and being laid at the bottom of ceramic crucible Portion, is placed in the middle part of tube furnace by this porcelain crucible, is then removed the inner air of tube furnace by evacuation, carries out with high pure nitrogen Displacement, is repeated 3 times to ensure sufficient oxygen-free environment, the flow speed control of nitrogen is at 80ml per minute, and programming rate is 5 DEG C per second, First stop 2 hours at 150 DEG C, after be pyrolyzed 5 hours under the conditions of 1100 DEG C, obtain metal@carbon composite.
Repeat step (4) and step (5) in embodiment 1, and the carbon-based nano composite for electrode is carried out transmitted electron Microscope characterizes and performance of lithium ion battery characterizes.
Embodiment 4:
[Ni is prepared by step (1) and (2) in embodiment 12(L-asp)2(bpy)] crystal powder material.
[the Ni that will synthesize2(L-asp)2(bpy)] crystal powder is lightly ground to existing without larger particles and being laid at the bottom of ceramic crucible Portion, is placed in the middle part of tube furnace by this porcelain crucible, is then removed the inner air of tube furnace by evacuation, carries out with high pure nitrogen Displacement, is repeated 3 times to ensure sufficient oxygen-free environment, the flow speed control of nitrogen is at 80ml per minute, and programming rate is 5 DEG C per second, First stop 2 hours at 150 DEG C, after be pyrolyzed 2 hours under the conditions of 1000 DEG C, obtain metal@carbon composite.
By step (4) preparation in embodiment 1 for the carbon-based nano composite of electrode.
Embodiment 5:
[Ni is prepared by step (1) and (2) in embodiment 12(L-asp)2(bpy)] crystal powder material.
[the Ni that will synthesize2(L-asp)2(bpy)] crystal powder is lightly ground to existing without larger particles and being laid at the bottom of ceramic crucible Portion, is placed in the middle part of tube furnace by this porcelain crucible, is then removed the inner air of tube furnace by evacuation, carries out with high pure nitrogen Displacement, is repeated 3 times to ensure sufficient oxygen-free environment, the flow speed control of nitrogen is at 80ml per minute, and programming rate is 5 DEG C per second, First stop 2 hours at 150 DEG C, after be pyrolyzed 8 hours under the conditions of 900 DEG C, obtain metal@carbon composite.
By step (4) preparation in embodiment 1 for the carbon-based nano composite of electrode.
Embodiment 6:
[Ni is prepared by step (1) and (2) in embodiment 12(L-asp)2(bpy)] crystal powder material.
[the Ni that will synthesize2(L-asp)2(bpy)] crystal powder is lightly ground to existing without larger particles and being laid at the bottom of ceramic crucible Portion, is placed in the middle part of tube furnace by this porcelain crucible, is then removed the inner air of tube furnace by evacuation, carries out with high pure nitrogen Displacement, is repeated 3 times to ensure sufficient oxygen-free environment, the flow speed control of nitrogen is at 80ml per minute, and programming rate is 5 DEG C per second, First stop 2 hours at 150 DEG C, after be pyrolyzed 5 hours under the conditions of 600 DEG C, obtain metal@carbon composite.
Repeat step (4) and step (5) in embodiment 1, and the carbon-based nano composite for electrode is carried out transmitted electron Microscope characterizes and performance of lithium ion battery characterizes.
From figure 1 it appears that [the Ni of synthesis in embodiment 12(L-asp)2(bpy)] there is feature near 7.96 ° in crystal powder The series of features peak occurred after peak and 10 ° all with the X-ray diffraction spectrogram (simulation softward: Mercury 3.3) of simulation Fit like a glove, there is no the appearance of any impurity peaks, [the Ni of synthesis is described2(L-asp)2(bpy)] crystal powder is pure phase, diffraction maximum The crystallization degree that high intensity also demonstrates crystal powder is the highest.
From figure 2 it can be seen that [the Ni of synthesis in embodiment 12(L-asp)2(bpy)] crystal powder had 3% before 150 DEG C Weightlessness, the water adsorbed in deriving from sample surfaces and duct.Crystal powder starts to decompose, when 440 DEG C at about 300 DEG C Decomposing completely, during this weightless 70%, deriving from structure the element transformations such as carbon oxygen is the loss of gas.Higher than 440 DEG C Temperature range quality substantially tend towards stability.
From figure 3, it can be seen that [the Ni of synthesis in embodiment 1～32(L-asp)2(bpy)] crystal powder shape after experience high temperature pyrolysis Having become carbon-based nano composite, be made up of the nanometer bead (6～20nm) of a large amount of size uniforms, what this nanometer bead had is Graphited carbon ghost, have for nucleocapsid structure, its internal core is metallic nickel simple substance.Along with the rising of pyrolysis temperature, graphite The ratio occupied by carbon ghost changed also is more and more higher.This microstructure ensure that such carbon-based nano composite lithium from Superior function on sub-battery electrode material.
Figure 4, it is seen that the carbon-based nano composite for electrode of preparation is at electric current 100mA g in embodiment 1-1 Under the conditions of record first lap electric discharge and charging capacity be respectively 525mAh/gh and 255mAh/gh.From the beginning of the second circle, along with Increasing of cycle-index, electric discharge becomes the trend of slowly rising with charging capacity, and when circulating for 100 times, electric discharge and charging capacity are divided Do not reach 370mAh/gh and 360mAh/gh, be sufficiently close to the theoretical capacity of graphite cathode material.Along with cycle-index Increasing, the biggest probability of its performance can become more preferable, have the highest stability, this is in lithium ion battery electrode material field It is uncommon, is a very promising class new material.
From figure 5 it can be seen that the carbon-based nano composite for electrode of preparation is at electric current 100mA g in embodiment 2-1 Under the conditions of record first lap electric discharge and charging capacity be respectively 433mAh/gh and 202mAh/gh.From the beginning of the second circle, with Increasing of cycle-index, electric discharge becomes the trend of slowly rising with charging capacity, when circulating for 100 times, and electric discharge and charging capacity Respectively reach 284mAh/gh and 278mAh/gh, there is good stability equally, be a very promising class Novel lithium from Sub-battery electrode material.
From fig. 6 it can be seen that the carbon-based nano composite for electrode of preparation is at electric current 100mA g in embodiment 3-1 Under the conditions of record first lap electric discharge and charging capacity be respectively 258mAh/gh and 93mAh/gh.From the beginning of the second circle, along with Increasing of cycle-index, electric discharge becomes the trend of slowly rising with charging capacity, and when circulating for 100 times, electric discharge and charging capacity are divided Do not reach 274mAh/gh and 270mAh/gh, there is good stability equally, be a very promising class new type lithium ion Battery electrode material.
It can be seen from figure 7 that the carbon-based nano composite for electrode of preparation is at electric current 100mA g in embodiment 4-1 Under the conditions of record first lap electric discharge and charging capacity be respectively 380mAh/gh and 255mAh/gh.From the beginning of the second circle, with Increasing of cycle-index, electric discharge becomes the trend of slowly rising with charging capacity, when circulating for 100 times, and electric discharge and charging capacity Respectively reach 358mAh/gh and 356mAh/gh, there is good stability equally, be a very promising class Novel lithium from Sub-battery electrode material.
As can be seen from Figure 8, the carbon-based nano composite for electrode prepared in embodiment 5 is at electric current 100mA g-1 Under the conditions of record first lap electric discharge and charging capacity be respectively 341mAh/gh and 135mAh/gh.From the beginning of the second circle, with Increasing of cycle-index, electric discharge becomes the trend of slowly rising with charging capacity, when circulating for 100 times, and electric discharge and charging capacity Respectively reach 272mAh/gh and 267mAh/gh, there is good stability equally, be a very promising class Novel lithium from Sub-battery electrode material.
It can be seen in figure 9 that the carbon-based nano composite for electrode of preparation is at electric current 100mA g in embodiment 6-1 Under the conditions of record first lap electric discharge and charging capacity be respectively 258mAh/gh and 93mAh/gh.From the beginning of the second circle, along with Increasing of cycle-index, electric discharge becomes the trend of slowly rising with charging capacity, and when circulating for 100 times, electric discharge and charging capacity are divided Do not reach 274mAh/gh and 269mAh/gh, there is good stability equally, be a very promising class new type lithium ion Battery electrode material.
Description to the embodiment that disclosed in this invention is not intended to limit the scope of the present invention, but is used for describing the present invention. Correspondingly, the scope of the present invention is not limited by embodiment of above, but is defined by claim or its equivalent.

Claims (10)

1., for a carbon-based nano composite for electrode, described carbon-based nano composite is that employing includes metal-organic bone The compound of frame, under inert protective atmosphere, high temperature pyrolysis obtains.
2. the carbon-based nano composite described in claim 1, it is characterised in that the compound of described metal-organic framework For, the two-dimensional layer compound that metallic compound and Organic substance are formed, and the three-dimensional framework built by the pillared effect of organic ligand Structure.
3. the carbon-based nano composite of claim × described, it is characterised in that described metal-organic framework compound is [Ni2(L-asp)2(bpy)]·CH3OH·H2O, is that the two-dimensional layer compound formed by basic nickel carbonate and aspartic acid L-asp leads to Cross organic ligand 4,4'-and connect the three dimensional skeletal structure that the pillared effect of pyridine is built.
4. the carbon-based nano composite of claim × described, it is characterised in that the duct size of described three dimensional skeletal structure For
5., according to the preparation method of the carbon-based nano composite for electrode described in any one of claim 1-4, its feature exists In, described preparation method comprises the following steps:
(1)Ni(L-asp)(H2O)2Preparation: by NiCO3·2Ni(OH)2·xH2O, L-asp and H2O 1:(0.5 in mass ratio～3): (100～500) mix, and heated and stirred 0.5～5 hours under the conditions of being maintained at 60～100 DEG C, to major part powder soluble in water after Stop heating and stirring；Filtration removes the insoluble matter in solution and obtains settled solution, and puts into standing in 60～120 DEG C of baking ovens 0.5～2 day, after aqueous solvent volatilization completely, i.e. obtain green Ni (L-asp) (H2O)2Crystal；
(2)[Ni2(L-asp)2(bpy)] the preparation of crystalline material: Ni (the L-asp) (H that step (1) is obtained2O)2Join methanol With in the mixed solution of water, continuing to add 4 under agitation after being partly dissolved, 4'-connects pyridine so that each material in final solution Mass ratio be Ni (L-asp) (H2O)2: 4,4'-connects pyridine: methanol: water=1:0.5～10:1～80:1～80；This solution is turned Move to autoclave seals, crystallization 1～4 days in 80～180 DEG C of baking ovens；After question response still is cooled to room temperature, by filtering, Wash and be dried to obtain aeruginous [Ni2(L-asp)2(bpy)] crystal powder；
(3) preparation of carbon-based nano the composite: [Ni that step (2) is synthesized2(L-asp)2(bpy)] crystal powder grinds To existing without larger particles and being laid in bottom ceramic crucible, this porcelain crucible is placed in the middle part of tube furnace, is then removed by evacuation Remove the inner air of tube furnace, replace with high pure nitrogen, repeat 2～5 times to ensure sufficient oxygen-free environment, After being pyrolyzed 2～8 hours under the conditions of 600～1200 DEG C, obtain metal@carbon composite；After concentrated hydrochloric acid processes 1～5 day, use Deionized water wash 3～6 times, separate and obtain the carbon-based nano composite for electrode after drying.
Method for electrode the most according to claim 5, it is characterised in that by room temperature to pyrolysis in described step (3) Temperature uses temperature programming, and programming rate is 2～10 DEG C per second.
Method for electrode the most according to claim 5, it is characterised in that in described step (3) temperature-rise period [Ni2(L-asp)2(bpy)] crystal powder stops 0.5～4 hour at 100～200 DEG C in temperature-rise period, to remove plane of crystal and hole The solvent molecule of residual in road.
Method the most according to claim 5, it is characterised in that the flow velocity of nitrogen is controlled by suspended body flowmeter, stream Speed is per minute 20～120ml.
Method the most according to claim 5, it is characterised in that described concentrated hydrochloric acid processing mode is to be soaked completely by powder body material Among concentrated hydrochloric acid.
10. according to method described in the material described in any one of claim 1-4, any one of claim 5-9 prepare for electrode Carbon-based nano composite in the application of lithium ion battery electrode material.
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