CN104466102A - Porous V2O5/C composite microspheres of lithium secondary battery positive electrode material and preparation method of porous V2O5/C composite microspheres - Google Patents

Porous V2O5/C composite microspheres of lithium secondary battery positive electrode material and preparation method of porous V2O5/C composite microspheres Download PDF

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CN104466102A
CN104466102A CN201410635144.4A CN201410635144A CN104466102A CN 104466102 A CN104466102 A CN 104466102A CN 201410635144 A CN201410635144 A CN 201410635144A CN 104466102 A CN104466102 A CN 104466102A
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pmma
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CN104466102B (en
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李朝晖
肖放
雷钢铁
肖启振
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Xiangtan University
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/133—Electrodes based on 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on 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

Abstract

The invention discloses porous V2O5/C composite microspheres of a lithium secondary battery positive electrode material and a preparation method of the porous V2O5/C composite microspheres. The porous V2O5/C composite microspheres are formed by clustering carbon coated V2O5 nano composite particles with the particle sizes of 5-30 mirons, and the porous V2O5/C composite microspheres are internally provided with porous structures. The preparation method comprises the following steps of synthesizing crosslinked polymethyl methacrylate PMMA microgel spheres, hydrolyzing partially so as to act as a mold plate for synthesizing the porous V2O5/C composite microspheres; adsorbing VO<2+> to three-dimensional meshes of the PMMA mold plate, changing the pH value of an adsorption solution, hydrolyzing the VO<2+> to generate V2O5 nano particles, and filling the three-dimensional meshes in situ with the V2O5 nano particles so as to obtain a V2O5/PMMA precursor; and forging the precursor so as to obtain the porous V2O5/C composite microspheres. The composite microsphere has the beneficial effects of improving the multiplying performance and the cycle performance and the like; the preparation method is simple in technology, and is suitable for being used in large-scale industrial production.

Description

A kind of positive electrode material of lithium secondary cell porous V 2o 5/ C complex microsphere and preparation method thereof
technical field
The invention belongs to field of chemical power source, relate to a kind of lithium battery material and preparation method thereof, especially a kind of positive electrode material of lithium secondary cell porous V 2o 5/ C complex microsphere and preparation method thereof.
Background technology
In recent years, industry soars with economic high speed and makes energy problem very outstanding, and development new forms of energy are one of significant problems that must solve 21 century, therefore, people's Devoting Major Efforts To Developing water energy, wind energy, nuclear energy and solar energy equal energy source, finally export with electrical energy form and be used widely.In addition, the chemical power sources such as lead-acid battery, Ni-MH battery, lithium ion battery, based on redox reaction, export electric energy to applied load, are widely used in electric automobile, electric tool and portable electric appts.Compared to lead-acid battery and Ni-MH battery, lithium ion battery has the features such as the large and environmental pollution of operating voltage high (3.6 V), energy density is little, extensive use in the walkie electronic apparatus such as mobile phone, Digital Video, notebook computer, panel computer, electric tool.Wherein, the specific capacity of the carbon negative pole material that lithium ion battery uses generally is no more than 400 mAh/g, improve the energy density of battery, must use the electrode material that specific capacity is high, comprise positive electrode and negative material.
Because lithium metal has extremely low hydrogen mark reducing electrode electromotive force-3.06 V (vs. NHE) and high electrochemical specific capacity 3860 mAh/g, therefore, using the lithium secondary battery that lithium metal is negative pole to have higher energy density, is the Green Chemistry power supply with long-range development prospect.Along with deepening continuously of research, people are after the lithium dendrite arm problem solving lithium secondary battery and safe application performance, lithium secondary battery can be widely used as the portable power source of a large amount of electronic and electrical equipment, even can be used as the chemical power source of electric automobile, large-scale batch (-type) energy storage device (wind energy, solar energy).In the lithium secondary battery, the quality of chemical property to battery properties (energy density, cycle life, high rate performance etc.) of positive electrode plays key effect, therefore, synthesize energy density high, to have extended cycle life and the cheap positive electrode of high rate performance excellence becomes the vital task of current scientific worker.
Up to now, in numerous anode material for lithium-ion batteries, cobalt acid lithium (LiCoO 2), lithium manganate having spinel structure (LiMn 2o 4), nickle cobalt lithium manganate (LiNi (1-x-y)co xmn yo 2) and LiFePO 4 (LiFePO 4) etc. industrial applications, the specific capacity of its practical application is all no more than 200 mAh/g, but also more or less there are some problems, and the price of such as cobalt is high, poisonous, cobalt acid lithium poor heat stability; The problems of dissolution of manganic in electrolyte solution, high temperature cyclic performance is poor; The bulk density of LiFePO 4 is low, poorly conductive etc., forces people constantly to research and develop high-performance positive electrode that is novel, cheap, environmental protection.Fortunately, based on the positive electrode material of lithium secondary cell of polyelectron reaction, stratiform α-V 2o 5at 1.5 ~ 4 V(vs. Li +/ Li) voltage range, embed Li continuously +during ion, the repeatedly phase in version of experience α → ε → δ → γ → ω, every mole of V 2o 53 moles of Li can be embedded +ion, has the theoretical specific capacity of 441 mAh/g.Concrete electrochemical reaction is as follows:
α-V 2O 5 + 0.7Li ++ 0.7e -→ ε-Li 0.7V 2O 5①
ε-Li 0.7V 2O 5 + 0.3Li ++ 0.3e - → δ-LiV 2O 5②
δ-LiV 2O 5 + Li ++ e - → γ-Li 2V 2O 5 ③
γ-Li 2V 2O 5 + Li ++ e - → ω-Li 3V 2O 5 ④
Research shows, V 2o 5when being discharged to 1.5 V, form ω-Li 3v 2o 5, it is difficult to all to take off lithium and generates α-V in charging process subsequently 2o 5, irreversible phase transition occurs, causes its capacity sharp-decay, cycle performance worsens.If V 2o 51., 2., 3. experience wherein walks reaction (namely in 2 ~ 4 V scope discharge and recharges), reversible phase in version occurs, every mole of V 2o 5the electrochemical reaction of 2 electronics can be realized, the theoretical specific capacity of 294 mAh/g can be obtained.And China has abundant navajoite resource, development of new V 2o 5positive electrode has advantageous advantage and actual application value.But, V 2o 5lithium ion diffusion coefficient (10 -12cm 2/ s) and electronic conductivity (10 -2~ 10 -3s/cm) lower, be difficult to the requirement meeting fast charging and discharging.And based on the electrochemical reaction of embedding lithium, the migration rate of electronics and ion determines the kinetics of electrode process of electrode material.Therefore, the V of three-dimensional ion/electron conduction is synthesized 2o 5electrode material, can improve its energy density and power density.
People are improving V 2o 5the chemical property aspect of positive electrode, does a lot of work.Such as, application number is that the Chinese patent application of CN201210262737.1 provides a kind of V 2o 5the preparation method of nano material, the method forms peroxide vanadic acid by hydrogen peroxide solution barium oxide being added certain mass mark, heat drying forms gel again, again gel is sintered obtained vanadium pentoxide nanometer material in atmosphere, the standby vanadic oxide nano anode material of this legal system is in 4-2.1V voltage range, and with the electric discharge of 0.05A/g current density, specific capacity is 264 mAh/g, after 50 circulations, capability retention is more than 90%, but its times of forthright improvement situation is unclear.Application number is that the Chinese patent application of CN201310080001.7 provides a kind of modification V 2o 5the preparation method of material, the method adopts soluble lithium salt in water heating kettle to V 2o 5carry out pre-embedding lithium, carry out modification from structure and pattern.Resulting materials, in 4-2.5V voltage range, discharges with the current density of 0.03A/g, and specific capacity is 215 mAh/g, and after 200 circulations, capability retention is 99%; Discharge with the current density of 3A/g, specific capacity is 140 mAh/g, but the improvement of its cycle performance is in confused situation.Although V 2o 5can improve its chemical property to a certain extent after material nano, but sol-gel process and hydro-thermal reaction method not only synthesis technique are complicated, and the structure of more difficult control product in preparation process, be difficult to large-scale industrial production.
 
Summary of the invention
the object of the invention is to,for the deficiencies in the prior art, provide a kind of positive electrode material of lithium secondary cell porous V 2o 5/ C complex microsphere and preparation method thereof.
implementing technical scheme of the present invention is,a kind of positive electrode material of lithium secondary cell porous V 2o 5/ C complex microsphere, the V coated by carbon 2o 5nano composite granules gathering forms, and its particle diameter is 5 ~ 30 μm, and inside has graded porous structure, electroactive substance V 2o 5mass fraction be 75 ~ 85%; Wherein, the particle diameter of Nano composite granules is 10 ~ 30 nm;
A kind of positive electrode material of lithium secondary cell porous V 2o 5the preparation method of/C complex microsphere, comprises the following steps and method:
Step one, adopts emulsion method to be polymerized synthesizing cross-linked PMMA microgel ball, generates carboxyl (-COO after partial hydrolysis -) group, utilize electrostatic attraction effect, by VO 2+be adsorbed onto in the three-dimensional mesh of its inside; In deionized water, add surfactant, methyl methacrylate MMA monomer and n,N'-methylene bisacrylamide amine amide MBA crosslinking agent, after stirring, more slowly adds oxidizing agent solution; After logical nitrogen deoxygenation 1h, raise temperature to 65 ~ 75 DEG C of reaction system, and condensing reflux 2 ~ 3 h under nitrogen protection, obtain milky mixed liquor; After filtration, gained powder water and ethanol wash 2 ~ 3 times, obtain the PMMA microsphere be cross-linked; Again PMMA microsphere is reacted 0.5h in strong alkali solution, after washing 3 times, the dry 24h of room temperature in vacuo, obtains the PMMA microsphere template be cross-linked;
Step 2, changes the pH value in adsorption liquid, VO 2+hydrolysis generates V 2o 5nano particle in situ is filled in three-dimensional mesh, obtains V 2o 5/ PMMA presoma; At oxalic acid (H 2c 2o 4) solution in, add ammonium metavanadate NH 4vO 3, abundant stirring and dissolving; Then the PMMA microsphere template of step one gained is added; At 60 ~ 80 DEG C, low rate mixing reaction 12 ~ 36h, filter, filter cake 80 ~ 90 DEG C of freeze-day with constant temperature, obtain V 2o 5/ PMMA presoma;
Step 3, calcines V in inert atmosphere 2o 5/ PMMA presoma, makes the PMMA strand carbonization in presoma, obtains porous V 2o 5/ C complex microsphere; Gained presoma in step 2 is placed in ceramic crucible, puts into tube-type atmosphere furnace, after logical nitrogen, heat up at a slow speed calcine by steps, and cool at a slow speed with stove, synthesizing porous V 2o 5/ C complex microsphere;
Further, described methyl methacrylate with n, n'-methylene bisacrylamide amine amide is preferred (20 ~ 30) in mass ratio: 1; Preferred 1:(1.2 ~ 1.5 of mol ratio of ammonium metavanadate and oxalic acid);
Described oxidant is one or more in potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate, and oxidant concentration optimum is 0.1 mol/L, 20% ~ 50% of consumption preferred MMA monomer molar amount;
Described strong alkali solution is one or more in lithium hydroxide, NaOH and potassium hydroxide, and concentration is 0.05 ~ 0.2 mol/L preferably;
Described concentration of oxalic acid is 0.4 ~ 0.6 mol/L preferably;
Further, described methyl methacrylate with n, n'-methylene bisacrylamide amine amide in mass ratio optimum is 25:1; The mol ratio optimum of ammonium metavanadate and oxalic acid is 1:1.3;
Further, described oxidant consumption optimum is 30% of MMA monomer molar amount;
Further, surfactant is one or more in dodecyl sodium sulfate, sodium cetanesulfonate, neopelex and 18 hard fatty acids sodium, and addition is preferably 0.05 ~ 0.1 g/L of liquor capacity;
Further, strong alkali solution concentration optimum is 0.1 mol/L;
Further, concentration of oxalic acid optimum is 0.5 mol/L;
Further, segmentation at a slow speed intensification calcining manners is: first optimum in atmosphere to Optimal Temperature 200 DEG C, keeps 1h optimal time with 0.5 DEG C/min ramp; Optimal Temperature 350 DEG C is warming up to the optimal rate of 0.2 DEG C/min again, insulation 1h optimal time in nitrogen; Finally in nitrogen, be warming up to Optimal Temperature 500 DEG C sintering 2h optimal time with the optimal rate of 0.5 DEG C/min, be cooled to room temperature at a slow speed with stove.
Beneficial effect of the present invention is:
1, polymer microgel is the macromolecule spherical particle that a class has the intramolecular crosslinking of three-dimensional net structure, utilize its distinctive three-dimensional network space structure, presoma ion is introduced microgel inner, then precipitation, reduction or oxidation reaction is started, in-situ preparation inorganic nano-particle, thus the inorganic-organic composite material obtaining nanoscale compound.The present invention selects methyl methacrylate to be the PMMA microsphere that monomer synthesize is cross-linked, and generates electronegative-COO after partial hydrolysis -group, utilizes electrostatic attraction effect, will have electropositive presoma ion VO 2+introducing PMMA microsphere is inner, in-situ preparation V 2o 5nano particle.By the three-dimensional mesh structure Effective Regulation V of polymetylmethacrylate template 2o 5the particle diameter of nano particle and pattern, optimize V 2o 5the physics of nano particle and chemical property.
2, porous V 2o 5the loose structure of/C complex microsphere, can cushion Li on the one hand +embed-deviate from the V caused in process 2o 5the change in volume of crystal, can adsorb a large amount of electrolyte solution on the other hand, be V 2o 5nano particle provides the Li needed for embedding-dealkylation reaction in time +source, forms Li +migrating channels.Therefore, porous V 2o 5/ C complex microsphere has three-dimensional ionic conduction network, Li +diffusion coefficient is improved, and improves V 2o 5the kinetics of electrode process of positive electrode.
3, porous V 2o 5v in/C complex microsphere 2o 5nano particle is coated by amorphous carbon, and these nano-carbon layers can electronics fast needed for delivery electrodes reaction, forms electron transfer passage.In addition, nano-carbon layer can isolate V 2o 5nano particle contacts with the direct of electrolyte solution, reduces V 2o 5the dissolution degree of nano particle in electrolyte solution.Therefore, porous V 2o 5/ C complex microsphere has three-dimensional electronic conductive network, improves its high rate performance and cycle performance.
4, preparation method's technique of the present invention is simple, and easily controls the structure of product, is applicable to large-scale industrial production.
accompanying drawing explanation
Fig. 1 is positive electrode material of lithium secondary cell porous V prepared by the present invention 2o 5the X-ray diffractogram of/C complex microsphere.Instrument used in the present invention is German Bruker D8 polycrystal powder Advanced Diffraction instrument, measurement environment: Cu K α radiation source (λ=1.5406), 45 kV operating voltages, 50 mA operating currents, sweep speed is 2o/min, and scanning angle 2 θ is 10o-90o.The V of synthesis 2o 5the feature crystal face peak that material is all and standard spectrogram (JCPDS no. 41-1426) basically identical, do not find obvious impurity peaks, show that products therefrom is rhombic system V 2o 5.
Fig. 2 is positive electrode material of lithium secondary cell porous V prepared by the present invention 2o 5scanning electron microscopy (SEM) figure of/C complex microsphere.As seen from the figure, V 2o 5/ C complex microsphere has spherical morphology, and particle size range is 5 ~ 30 μm, and the nano particle that microballoon is 10 ~ 30 nm by particle diameter is formed, and has loose structure.
Fig. 3 is that the present invention prepares positive electrode material of lithium secondary cell porous V 2o 5scanning electron microscopy (SEM) single enlarged drawing of/C complex microsphere.
Fig. 4 is lithium ion anode material porous V prepared by the present invention 2o 5/ C complex microsphere is at room temperature with the discharge curve first of different multiplying.
Fig. 5 is lithium ion anode material porous V prepared by the present invention 2o 5the cycle performance curve of/C complex microsphere under different multiplying.
Embodiment
In conjunction with the embodiments and accompanying drawing the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
(1), the preparation of PMMA microsphere template.In the there-necked flask filling 125 ml deionized waters, add 0.01g dodecyl sodium sulfate (SDS), 1.7496g methyl methacrylate (MMA) and 0.0933g n,N'-methylene bisacrylamide amine amide (MBA), after mechanical agitation is even, more slowly adds the 5mL solution containing 0.14g potassium peroxydisulfate (KPS).After logical nitrogen deoxygenation 1h, raise temperature to 65 ~ 75 DEG C of reaction system, and condensing reflux 2 ~ 3 h under nitrogen protection, obtain milky mixed liquor.After filtration, powder water and ethanol wash 2 ~ 3 times, obtain the PMMA microgel ball be cross-linked.Finally, PMMA microsphere is reacted 0.5h in the lithium hydroxide solution of 0.5 mol/L, after washing 3 times, the dry 24h of room temperature in vacuo, obtains the PMMA microsphere template be cross-linked.
(2), presoma V 2o 5the preparation of/PMMA.1.17g oxalic acid (H is contained at 100 ml 2c 2o 4) solution in, add 1.17g ammonium metavanadate (NH 4vO 3), abundant stirring and dissolving, solution colour is by yellow (VO 3 -) change blueness (VO into 2 +).In above-mentioned blue solution, add the PMMA microsphere template of 0.1g step (1) gained, utilize carboxyl (-COO in PMMA microgel ball -) group and VO 2+between electrostatic attraction effect, by VO 2+be adsorbed in the three-dimensional mesh of PMMA microgel ball.At 60 ~ 80 DEG C, low rate mixing reaction 12 ~ 36h, filter, filter cake 80 ~ 90 DEG C of dryings, obtain V 2o 5/ PMMA presoma.
(3), porous V 2o 5the preparation of/C complex microsphere.Gained presoma in step (2) is placed in ceramic crucible, puts into tube-type atmosphere furnace, elder generation with 0.5 DEG C/min ramp to 200 DEG C, keeps 1h in air atmosphere; Logical nitrogen is after 10 minutes again, with 0.2 DEG C/min ramp to 350 DEG C, and insulation 1h; Finally with 0.2 DEG C/min ramp to 500 DEG C sintering 20h, cool at a slow speed with stove, synthesizing porous V 2o 5/ C complex microsphere.By analysis, porous V 2o 5electroactive substance V in/C complex microsphere 2o 5mass fraction be 82%.
Porous V prepared by the present embodiment 2o 5/ C complex microsphere, acetylene black and Kynoar are scattered in mass ratio 8.5:0.5:1 nin-methyl pyrrolidone, stir form slurry at normal temperatures and pressures, be evenly coated in aluminium foil surface, 120 DEG C of vacuumizes, after roll-in, be cut into the thin rounded flakes that diameter is 1 cm, average load 3.8 mg V on every plate electrode 2o 5electroactive substance.With it for positive pole, assemble button cell with cathode of lithium and Celgard 2300 perforated membrane, electrolyte is the LiPF of 1 mol/L 6ethylene carbonate (EC) and dimethyl carbonate (DMC) solution (both mass ratioes are 1:1).
Use constant current charge-discharge technology to test above-mentioned button cell, probe temperature is 25 DEG C, and end of charge voltage is 4 V, and final discharging voltage is 2 V.Respectively with 0.1C, 0.5C, 2C, 5C and 10C(1C=294 mA/g) discharge and recharge, V 2o 5the first discharge specific capacity of electroactive substance is respectively 291,264,240,191 and 166 mAh/g; It circulates after 300 times with 0.5C, 5C and 10C respectively, and specific discharge capacity is respectively 238,147 and 105 mAh/g, and capability retention is respectively 90%, 77% and 63%.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.Be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will not be restricted to embodiment illustrated herein, but the scope consistent with principle disclosed herein and novelty.

Claims (9)

1. a positive electrode material of lithium secondary cell porous V 2o 5/ C complex microsphere, is characterized in that, the V coated by carbon 2o 5nano composite granules gathering forms, and its particle diameter is 5 ~ 30 μm, and inside has graded porous structure, electroactive substance V 2o 5mass fraction be 75 ~ 85%; Wherein, the particle diameter of Nano composite granules is 10 ~ 30 nm.
2. a positive electrode material of lithium secondary cell porous V 2o 5the preparation method of/C complex microsphere, is characterized in that, comprises the following steps and method:
Step one, adopts emulsion method to be polymerized synthesizing cross-linked PMMA microgel ball, generates carboxyl (-COO after partial hydrolysis -) group, utilize electrostatic attraction effect, by VO 2+be adsorbed onto in the three-dimensional mesh of its inside; In deionized water, add surfactant, methyl methacrylate MMA monomer and n,N'-methylene bisacrylamide amine amide MBA crosslinking agent, after stirring, more slowly adds oxidizing agent solution; After logical nitrogen deoxygenation 1h, raise temperature to 65 ~ 75 DEG C of reaction system, and condensing reflux 2 ~ 3 h under nitrogen protection, obtain milky mixed liquor; After filtration, gained powder water and ethanol wash 2 ~ 3 times, obtain the PMMA microsphere be cross-linked; Again PMMA microsphere is reacted 0.5h in strong alkali solution, after washing 3 times, the dry 24h of room temperature in vacuo, obtains the PMMA microsphere template be cross-linked;
Step 2, changes the pH value in adsorption liquid, VO 2+hydrolysis generates V 2o 5nano particle in situ is filled in three-dimensional mesh, obtains V 2o 5/ PMMA presoma; At oxalic acid (H 2c 2o 4) solution in, add ammonium metavanadate NH 4vO 3, abundant stirring and dissolving; Then the PMMA microsphere template of step one gained is added; At 60 ~ 80 DEG C, low rate mixing reaction 12 ~ 36h, filter, filter cake 80 ~ 90 DEG C of freeze-day with constant temperature, obtain V 2o 5/ PMMA presoma;
Step 3, calcines V in inert atmosphere 2o 5/ PMMA presoma, makes the PMMA strand carbonization in presoma, obtains porous V 2o 5/ C complex microsphere; Gained presoma in step 2 is placed in ceramic crucible, puts into tube-type atmosphere furnace, after logical nitrogen, heat up at a slow speed calcine by steps, and cool at a slow speed with stove, synthesizing porous V 2o 5/ C complex microsphere.
3. positive electrode material of lithium secondary cell porous V as claimed in claim 2 2o 5the preparation method of/C complex microsphere, is characterized in that, described methyl methacrylate with n, n'-methylene bisacrylamide amine amide is (20 ~ 30) in mass ratio: 1; The mol ratio of ammonium metavanadate and oxalic acid is 1:(1.2 ~ 1.5);
Described oxidant is one or more in potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate, and oxidant concentration is 0.1 mol/L, and consumption is 20% ~ 50% of MMA monomer molar amount,
Described strong alkali solution is one or more in lithium hydroxide, NaOH and potassium hydroxide, and concentration is 0.05 ~ 0.2 mol/L;
Described concentration of oxalic acid is 0.4 ~ 0.6 mol/L.
4. positive electrode material of lithium secondary cell porous V as claimed in claim 3 2o 5the preparation method of/C complex microsphere, is characterized in that, described methyl methacrylate with n, n'-methylene bisacrylamide amine amide is 25:1 in mass ratio; The mol ratio of ammonium metavanadate and oxalic acid is 1:1.3.
5. positive electrode material of lithium secondary cell porous V as claimed in claim 3 2o 5the preparation method of/C complex microsphere, is characterized in that, described oxidant consumption is 30% of MMA monomer molar amount.
6. positive electrode material of lithium secondary cell porous V as claimed in claim 2 2o 5the preparation method of/C complex microsphere, is characterized in that, surfactant is one or more in dodecyl sodium sulfate, sodium cetanesulfonate, neopelex and 18 hard fatty acids sodium, and addition is 0.05 ~ 0.1 g/L of liquor capacity.
7. positive electrode material of lithium secondary cell porous V as claimed in claim 3 2o 5the preparation method of/C complex microsphere, is characterized in that, strong alkali solution concentration is 0.1 mol/L.
8. positive electrode material of lithium secondary cell porous V as claimed in claim 3 2o 5the preparation method of/C complex microsphere, is characterized in that, concentration of oxalic acid is 0.5 mol/L.
9. positive electrode material of lithium secondary cell porous V as claimed in claim 2 2o 5the preparation method of/C complex microsphere, is characterized in that, segmentation at a slow speed intensification calcining manners is: first in atmosphere with 0.5 DEG C/min ramp to 200 DEG C, keeps 1h; Again in nitrogen with 0.2 DEG C/min ramp to 350 DEG C, insulation 1h; Finally in nitrogen, sinter 2h with 0.5 DEG C/min ramp to 500 DEG C, be cooled to room temperature at a slow speed with stove.
CN201410635144.4A 2014-11-13 2014-11-13 A kind of porous V2O5/C complex microspheres of positive electrode material of lithium secondary cell and preparation method thereof Expired - Fee Related CN104466102B (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105375004A (en) * 2015-10-23 2016-03-02 湘潭大学 Lithium secondary battery cathode material with long service life and high energy and preparation method thereof
CN106410178A (en) * 2016-11-30 2017-02-15 武汉理工力强能源有限公司 Preparation method and application of mesoporous vanadic oxide microspheres
CN106784738A (en) * 2017-02-13 2017-05-31 湘潭大学 A kind of mg-doped vanadic anhydride/carbon composite anode material and preparation method thereof
CN106935860A (en) * 2017-03-24 2017-07-07 华中科技大学 A kind of carbon intercalation V2O3Nano material, its preparation method and application
KR20200009202A (en) * 2018-07-18 2020-01-30 주식회사 엘지화학 Electrochemical pretreatment method of vanadium positive electrode for lithium secondary battery and vanadium positive electrode for lithium secondary battery pretreated by the same
CN111446442A (en) * 2020-02-29 2020-07-24 浙江工业大学 V-shaped groove2O5Preparation method and application of/C composite nanosheet material
CN112436116A (en) * 2020-11-18 2021-03-02 合肥国轩高科动力能源有限公司 Aluminum-doped ZnO film-coated ternary positive electrode @ C composite microsphere and preparation method and application thereof
CN113173600A (en) * 2021-05-08 2021-07-27 郑州轻工业大学 Preparation method and application of three-dimensional multi-channel hollow walnut-shaped vanadium dioxide @ carbon composite material
CN114068971A (en) * 2021-11-23 2022-02-18 成都先进金属材料产业技术研究院股份有限公司 Electrode for vanadium cell and vanadium cell

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102237523A (en) * 2010-05-06 2011-11-09 三星Sdi株式会社 Positive active material for rechargeable lithium battery and rechargeable lithium battery including same
CN102364728A (en) * 2011-11-02 2012-02-29 上海交通大学 Positive electrode material for lithium ion cells and preparation method thereof
US20130170098A1 (en) * 2008-08-15 2013-07-04 The Regents Of The University Of California Asymmetric hybrid supercapacitors based on nanotube nanowire composites

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130170098A1 (en) * 2008-08-15 2013-07-04 The Regents Of The University Of California Asymmetric hybrid supercapacitors based on nanotube nanowire composites
CN102237523A (en) * 2010-05-06 2011-11-09 三星Sdi株式会社 Positive active material for rechargeable lithium battery and rechargeable lithium battery including same
CN102364728A (en) * 2011-11-02 2012-02-29 上海交通大学 Positive electrode material for lithium ion cells and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
E. ARMSTRONG ET AL: "Investigations into structure and chemistry of 1D, 2D and 3D structured vanadium oxide nanomaterials for Li-ion batteries", 《ECS TRANSACTIONS 》 *
XIAOFEI ZHANG ET AL: "Carbon-Coated V2O5 Nanocrystals as High Performance Cathode Material for Lithium Ion Batteries", 《CHEM. MATER.》 *

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CN106410178A (en) * 2016-11-30 2017-02-15 武汉理工力强能源有限公司 Preparation method and application of mesoporous vanadic oxide microspheres
CN106410178B (en) * 2016-11-30 2019-04-26 武汉理工力强能源有限公司 A kind of preparation method and application of mesoporous vanadic anhydride micron ball
CN106784738A (en) * 2017-02-13 2017-05-31 湘潭大学 A kind of mg-doped vanadic anhydride/carbon composite anode material and preparation method thereof
CN106935860A (en) * 2017-03-24 2017-07-07 华中科技大学 A kind of carbon intercalation V2O3Nano material, its preparation method and application
CN106935860B (en) * 2017-03-24 2019-09-24 华中科技大学 A kind of carbon intercalation V2O3Nano material, preparation method and application
KR20200009202A (en) * 2018-07-18 2020-01-30 주식회사 엘지화학 Electrochemical pretreatment method of vanadium positive electrode for lithium secondary battery and vanadium positive electrode for lithium secondary battery pretreated by the same
CN111527628A (en) * 2018-07-18 2020-08-11 株式会社Lg化学 Electrochemical pretreatment method for vanadium positive electrode for lithium secondary battery and vanadium positive electrode for lithium secondary battery pretreated by said method
US11646402B2 (en) 2018-07-18 2023-05-09 Lg Energy Solution, Ltd. Method for electrochemical pretreatment of vanadium positive electrode for lithium secondary batteries and vanadium positive electrode for lithium secondary batteries pretreated thereby
EP3706211A4 (en) * 2018-07-18 2021-03-17 Lg Chem, Ltd. Method for electrochemical pretreatment of vanadium positive electrode for lithium secondary batteries and vanadium positive electrode for lithium secondary batteries pretreated thereby
KR102567962B1 (en) 2018-07-18 2023-08-16 주식회사 엘지에너지솔루션 Electrochemical pretreatment method of vanadium positive electrode for lithium secondary battery and vanadium positive electrode for lithium secondary battery pretreated by the same
CN111446442A (en) * 2020-02-29 2020-07-24 浙江工业大学 V-shaped groove2O5Preparation method and application of/C composite nanosheet material
CN111446442B (en) * 2020-02-29 2021-08-24 浙江工业大学 V-shaped groove2O5Preparation method and application of/C composite nanosheet material
CN112436116A (en) * 2020-11-18 2021-03-02 合肥国轩高科动力能源有限公司 Aluminum-doped ZnO film-coated ternary positive electrode @ C composite microsphere and preparation method and application thereof
CN112436116B (en) * 2020-11-18 2022-03-11 合肥国轩高科动力能源有限公司 Aluminum-doped ZnO film-coated ternary positive electrode @ C composite microsphere and preparation method and application thereof
CN113173600B (en) * 2021-05-08 2022-08-23 郑州轻工业大学 Preparation method and application of three-dimensional multi-channel hollow walnut-shaped vanadium dioxide @ carbon composite material
CN113173600A (en) * 2021-05-08 2021-07-27 郑州轻工业大学 Preparation method and application of three-dimensional multi-channel hollow walnut-shaped vanadium dioxide @ carbon composite material
CN114068971A (en) * 2021-11-23 2022-02-18 成都先进金属材料产业技术研究院股份有限公司 Electrode for vanadium cell and vanadium cell
CN114068971B (en) * 2021-11-23 2023-10-27 成都先进金属材料产业技术研究院股份有限公司 Electrode for vanadium battery and vanadium battery

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