CN104466102B - A kind of porous V2O5/C complex microspheres of positive electrode material of lithium secondary cell and preparation method thereof - Google Patents

A kind of porous V2O5/C complex microspheres of positive electrode material of lithium secondary cell and preparation method thereof Download PDF

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CN104466102B
CN104466102B CN201410635144.4A CN201410635144A CN104466102B CN 104466102 B CN104466102 B CN 104466102B CN 201410635144 A CN201410635144 A CN 201410635144A CN 104466102 B CN104466102 B CN 104466102B
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porous
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pmma
complex microspheres
positive electrode
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CN104466102A (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 present invention discloses a kind of porous V of positive electrode material of lithium secondary cell2O5/ C complex microspheres and preparation method thereof, porous V2O5/ C complex microspheres by carbon coating V2O5Nano composite granules aggregation is formed, and its particle diameter is 5~30 μm, and inside has loose structure.Preparation method includes：Synthesizing cross-linked polymetylmethacrylate microgel ball, is used as synthesizing porous V after partial hydrolysis2O5The template of/C complex microspheres；Adsorb VO2+To the three-dimensional mesh of PMMA templates, change the pH value in adsorption liquid, VO2+Hydrolysis generation V2O5In nano particle in situ filling three-dimensional mesh, V is obtained2O5/ PMMA presomas；Presoma is calcined, porous V is obtained2O5/ C complex microspheres.The complex microsphere of the present invention, which has, improves the beneficial effect such as high rate performance and cycle performance；Its preparation method technique is simple, is adapted to large-scale industrial production.

Description

A kind of porous V2O5/C complex microspheres of positive electrode material of lithium secondary cell and preparation method thereof
Technical field
The invention belongs to field of chemical power source, it is related to a kind of lithium battery material and preparation method thereof, especially a kind of lithium two The porous V of primary cell positive electrode2O5/ C complex microspheres and preparation method thereof.
Background technology
In recent years, industry soars with economic high speed make it that energy problem is very prominent, and development new energy is that 21 century must One of significant problem that must be solved, therefore, people's Devoting Major Efforts To Developing water energy, wind energy, nuclear energy and solar energy equal energy source, finally with electric energy Form is exported and is used widely.In addition, the electrochmical power source such as lead-acid battery, Ni-MH battery, lithium ion battery is to aoxidize Based on reduction reaction, electric energy is exported to applied load, is widely used in electric automobile, electric tool and portable electronic and sets It is standby.Compared to lead-acid battery and Ni-MH battery, lithium ion battery has operating voltage high（3.6 V）, energy density is big and ring The features such as border pollution is small, in portable electronics such as mobile phone, DV, notebook computer, panel computer, electric tools Extensive use in electrical equipment.Wherein, the specific capacity for the carbon negative pole material that lithium ion battery is used is usually no more than 400 mAh/g, Improve the energy density of battery, it is necessary to use the high electrode material of specific capacity, including positive electrode and negative material.
Because lithium metal has the extremely low V (vs. NHE) of hydrogen mark reducing electrode potential -3.06 and high electrochemistry ratio The mAh/g of capacity 3860, therefore, has higher energy density for the lithium secondary battery of negative pole using lithium metal, is with long-range The Green Chemistry power supply of development prospect.With deepening continuously for research, people are solving the problems, such as the lithium dendrite arm of lithium secondary battery After safe application performance, lithium secondary battery can be widely used as the portable power source of a large amount of electronic and electrical equipments, it might even be possible to As electric automobile, large-scale batch (-type) energy storage device（Wind energy, solar energy）Electrochmical power source.In the lithium secondary battery, positive pole material The chemical property of material is to battery properties（Energy density, cycle life, high rate performance etc.）Quality play key effect, Therefore, synthesis energy density is high, to have extended cycle life turn into current scientific worker with the excellent cheap positive electrode of high rate performance Vital task.
So far, in numerous anode material for lithium-ion batteries, cobalt acid lithium（LiCoO2）, lithium manganate having spinel structure （LiMn2O4）, nickle cobalt lithium manganate（LiNi(1-x-y)CoxMnyO2）And LiFePO 4（LiFePO4）Deng industrial applications, its The specific capacity of practical application is no more than 200 mAh/g, but also more or less there are problems that, the price height of such as cobalt, Poisonous, cobalt acid lithium heat endurance is poor；Problems of dissolution of the manganic in electrolyte solution, high temperature cyclic performance is poor；Ferrous phosphate Low, poorly conductive of bulk density of lithium etc., forces people constantly to research and develop new, cheap, environmentally friendly high-performance positive electrode.Luckily , the positive electrode material of lithium secondary cell reacted based on polyelectron, stratiform α-V2O5In 1.5 ~ 4 V（vs. Li+/Li）Voltage model Enclose, be consecutively embedded Li+During ion, α → ε → δ → γ → ω multiple phase in version, every mole of V are undergone2O53 moles of Li can be embedded in+Ion, the theoretical specific capacity with 441 mAh/g.Specific electrochemical reaction is as follows：
α-V2O5+ 0.7Li+ + 0.7e- → ε-Li0.7V2O5 ①
ε-Li0.7V2O5 + 0.3Li+ + 0.3e- → δ-LiV2O5 ②
δ-LiV2O5+ Li+ + e- → γ-Li2V2O5 ③
γ-Li2V2O5+ Li+ + e- → ω-Li3V2O5 ④
Research shows, V2O5When being discharged to 1.5 V, ω-Li are formed3V2O5, it is difficult to whole in subsequent charging process De- lithium generation α-V2O5, occur irreversible phase transition, cause its capacity sharp-decay, cycle performance deteriorates.If V2O5Undergo it In 1., 2., 3. step reaction（I.e. in 2 ~ 4 V scope discharge and recharges）, occur reversible phase in version, every mole of V2O52 electronics can be realized Electrochemical reaction, can obtain 294 mAh/g theoretical specific capacity.Moreover, China possesses abundant navajoite resource, develop new V2O5Positive electrode has advantageous advantage and actual application value.But, V2O5Lithium ion diffusion coefficient（10-12 cm2/s）And electronic conductivity（10-2~10-3S/cm）It is relatively low, it is difficult to meet the requirement of fast charging and discharging.And based on the electricity of embedding lithium The migration rate of chemical reaction, electronics and ion determines the kinetics of electrode process of electrode material.Therefore, synthesize it is three-dimensional from The V of son/electronic conduction2O5Electrode material, can improve its energy density and power density.
People are improving V2O5In terms of the chemical property of positive electrode, do a lot of work.For example, Application No. CN201210262737.1 Chinese patent application provides a kind of V2O5The preparation method of nano material, this method is by by vanadium Oxide adds the hydrogen peroxide solution formation peroxide vanadic acid of certain mass fraction, reheats drying and forms gel, then gel is existed Sintered in air and vanadium pentoxide nanometer material is made, vanadic anhydride nano anode material prepared by the method is in 4-2.1V voltages Scope, with 0.05A/g current densities discharge, specific capacity be 264 mAh/g, 50 times circulation after capability retention more than 90%, but its Forthright improvement situation is unclear again.Application No. CN201310080001.7 Chinese patent application provides a kind of modified V2O5 The preparation method of material, this method uses soluble lithium salt in water heating kettle to V2O5Pre- embedding lithium is carried out, it is enterprising from structure and pattern Row modification.Resulting materials are discharged in 4-2.5V voltage ranges with 0.03A/g current density, and specific capacity is 215 mAh/ G, capability retention is 99% after 200 circulations；Discharged with 3A/g current density, specific capacity is 140 mAh/g, but it is followed Ring performance improvement it is in confused situation.Although V2O5Its chemical property can be improved after material nano to a certain extent, but That not only synthesis technique is complicated for sol-gel process and hydro-thermal reaction method, and in preparation process more difficult control product structure, It is difficult to large-scale industrial production.
The content of the invention
It is an object of the invention to which there is provided a kind of positive electrode material of lithium secondary cell is porous in view of the shortcomings of the prior art V2O5/ C complex microspheres and preparation method thereof.
Implementing technical scheme of the present invention is, a kind of porous V of positive electrode material of lithium secondary cell2O5/ C is combined micro- Ball, by the V of carbon coating2O5Nano composite granules aggregation is formed, and its particle diameter is 5~30 μm, and inside has graded porous structure, electricity Chemically reactive substance V2O5Mass fraction be 75 ~ 85%；Wherein, the particle diameter of Nano composite granules is 10 ~ 30 nm；
A kind of porous V of positive electrode material of lithium secondary cell2O5The preparation method of/C complex microspheres, comprises the following steps and method：
Step one, synthesizing cross-linked PMMA microgel balls are polymerize using emulsion method, carboxyl is generated after partial hydrolysis（-COO-） Group, is acted on using electrostatic attraction, by VO2+It is adsorbed onto in its internal three-dimensional mesh；In deionized water, surface-active is added Agent, methyl methacrylate MMA monomers and N, N '-methylene bisacrylamide amine amide MBA crosslinking agents, after stirring, then slowly Add oxidizing agent solution；After logical nitrogen deoxygenation 1h, the temperature of rise reaction system is condensed to 65~75 DEG C, and under nitrogen protection Flow back 2~3 h, obtains milky mixed liquor；After filtering, gained powder is washed 2 ~ 3 times with water and ethanol, the PMMA being crosslinked Microballoon；PMMA microsphere is reacted into 0.5h in strong alkali solution again, after washing 3 times, room temperature in vacuo dries 24h, is crosslinked PMMA microsphere template；
Step 2, changes the pH value in adsorption liquid, VO2+Hydrolysis generation V2O5Nano particle in situ is filled in three-dimensional mesh In, obtain V2O5/ PMMA presomas；In oxalic acid (H2C2O4) solution in, add ammonium metavanadate NH4VO3, it is sufficiently stirred for dissolving； Then the PMMA microsphere template obtained by step one is added；At 60~80 DEG C, low rate mixing reacts 12~36h, filtering, filter cake 80 ~ 90 DEG C of freeze-day with constant temperature, obtain V2O5/ PMMA presomas；
V is calcined in step 3, inert atmosphere2O5/ PMMA presomas, make the PMMA strands in presoma be carbonized, obtain many Hole V2O5/ C complex microspheres；Gained presoma in step 2 is placed in ceramic crucible, is put into tube-type atmosphere furnace, leads to after nitrogen, Heat up at a slow speed calcine by steps, and is cooled down at a slow speed with stove, synthesizing porous V2O5/ C complex microspheres；
Further, the methyl methacrylate and N, N '-methylene bisacrylamide amine amide are preferred in mass ratio（20~ 30）：1；The mol ratio of ammonium metavanadate and oxalic acid preferably 1：（1.2~1.5）；
The oxidant is the one or more in potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate, and oxidant concentration is most Excellent is 0.1 mol/L, the 20% ~ 50% of the preferred MMA monomer molars amount of consumption；
The strong alkali solution is the one or more in lithium hydroxide, NaOH and potassium hydroxide, and concentration is preferred 0.05~0.2 mol/L；
The concentration of oxalic acid preferably 0.4~0.6 mol/L；
Further, it is 25 that the methyl methacrylate and N, N '-methylene bisacrylamide amine amide are optimal in mass ratio：1； The optimal mol ratio of ammonium metavanadate and oxalic acid is 1：1.3；
Further, the oxidizer is optimal for the 30% of MMA monomer molar amounts；
Further, surfactant is dodecyl sodium sulfate, sodium cetanesulfonate, neopelex and ten One or more in eight hard fatty acids sodium, addition is preferably 0.05 ~ 0.1 g/L of liquor capacity；
Further, it is 0.1 mol/L that strong alkali solution concentration is optimal；
Further, it is 0.5 mol/L that concentration of oxalic acid is optimal；
Further, heating calcining manners are at a slow speed for segmentation：First in atmosphere it is optimal be warming up to 0.5 DEG C/min speed it is optimal 200 DEG C of temperature, keeps 1h optimal times；350 DEG C of Optimal Temperature is warming up to 0.2 DEG C/min optimal rate in nitrogen again, It is incubated 1h optimal times；500 DEG C of sintering 2h of Optimal Temperature are finally warming up to 0.5 DEG C/min optimal rate in nitrogen optimal Time, room temperature is cooled at a slow speed with stove.
The beneficial effects of the present invention are：
1st, polymer microgel is the macromolecule spherical particle for the intramolecular crosslinking that a class has three-dimensional net structure, is utilized Its distinctive three-dimensional network space structure, presoma ion is introduced inside microgel, then starts precipitation, reduction or oxidation anti- Should, in-situ preparation inorganic nano-particle, so as to obtain the compound inorganic-organic composite material of nanoscale.The present invention selects methyl Methyl acrylate is the synthesizing cross-linked PMMA microsphere of monomer, and electronegative-COO is generated after partial hydrolysis-Group, is drawn using electrostatic Power is acted on, and will have electropositive presoma ion VO2+Introduce inside PMMA microsphere, in-situ preparation V2O5Nano particle.Pass through The three-dimensional mesh structure Effective Regulation V of polymetylmethacrylate template2O5The particle diameter and pattern of nano particle, optimization V2O5The physics and chemical property of nano particle.
2nd, porous V2O5The loose structure of/C complex microspheres, on the one hand can buffer Li+Caused by during insertion-abjection V2O5The Volume Changes of crystal, on the other hand can adsorb a large amount of electrolyte solutions, be V2O5Nano particle provides embedding-de- in time Li needed for reaction+Source, forms Li+Migrating channels.Therefore, porous V2O5/ C complex microspheres have three-dimensional ionic conduction network, Li+ Diffusion coefficient is improved, and improves V2O5The kinetics of electrode process of positive electrode.
3rd, porous V2O5V in/C complex microspheres2O5Nano particle is coated by amorphous carbon, and these nano-carbon layers can be fast Electronics needed for fast delivery electrodes reaction, forms electron transfer passage.In addition, nano-carbon layer can isolate V2O5Nanometer Grain is directly contacted with electrolyte solution, reduces V2O5Dissolution degree of the nano particle in electrolyte solution.Therefore, it is porous V2O5/ C complex microspheres have three dimensional electron conductive network, improve its high rate performance and cycle performance.
4th, the preparation method technique of the present invention is simple, and is easily controlled the structure of product, is adapted to large-scale industrial production.
Brief description of the drawings
Fig. 1 is the porous V of positive electrode material of lithium secondary cell prepared by the present invention2O5The X-ray diffractogram of/C complex microspheres.This Instrument used in invention is Germany's Bruker D8 polycrystal powder Advanced Diffraction instrument, measuring environment：Cu K α radiations source (λ= 1.5406), 45 kV operating voltages, 50 mA operating currents, sweep speed is 2o/min, and the θ of scanning angle 2 is 10o-90o.Close Into V2O5All feature crystal face peaks of material and standard spectrogram（JCPDS no. 41-1426）It is basically identical, do not find substantially Impurity peaks, show products therefrom be rhombic system V2O5。
Fig. 2 is the porous V of positive electrode material of lithium secondary cell prepared by the present invention2O5The SEM of/C complex microspheres （SEM）Figure.As seen from the figure, V2O5/ C complex microspheres have a spherical morphology, and particle size range is 5 ~ 30 μm, microballoon by particle diameter be 10 ~ 30 nm nano particle is constituted, and with loose structure.
Fig. 3 is that the present invention prepares the porous V of positive electrode material of lithium secondary cell2O5The SEM of/C complex microspheres （SEM）Single enlarged drawing.
Fig. 4 is the porous V of lithium ion anode material prepared by the present invention2O5/ C complex microspheres are at room temperature with different multiplying Discharge curve first.
Fig. 5 is the porous V of lithium ion anode material prepared by the present invention2O5Cyclicity of/C the complex microspheres under different multiplying Can curve.
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 to This.
（1）, PMMA microsphere template preparation.In the there-necked flask for filling 125 ml deionized waters, 0.01g 12 is added Sodium alkyl sulfonate (SDS), 1.7496g methyl methacrylates (MMA) and 0.0933g N, N '-methylene bisacrylamide amine amide (MBA) after, mechanical agitation is uniform, it is slow added into the 5mL solution containing 0.14g potassium peroxydisulfates (KPS).Logical nitrogen deoxygenation 1h Afterwards, the temperature of rise reaction system is to 65~75 DEG C, and the h of condensing reflux 2~3 under nitrogen protection, obtains the milky white mixture of colours Liquid.After filtering, powder is washed 2 ~ 3 times with water and ethanol, the PMMA microgel balls being crosslinked.Finally, by PMMA microsphere in 0.5 0.5h is reacted in mol/L lithium hydroxide solution, after washing 3 times, room temperature in vacuo dries 24h, the PMMA microsphere mould being crosslinked Plate.
（2）, presoma V2O5/ PMMA preparation.Contain 1.17g oxalic acid (H in 100 ml2C2O4) solution in, add 1.17g ammonium metavanadates (NH4VO3), dissolving is sufficiently stirred for, solution colour is by yellow (VO3 -) it is changed into blueness（VO2 +）.Above-mentioned 0.1g steps are added in blue solution（1）The PMMA microsphere template of gained, utilizes carboxyl in PMMA microgel balls（-COO-）Group With VO2+Between electrostatic attraction effect, by VO2+In the three-dimensional mesh for being adsorbed in PMMA microgel balls.At 60~80 DEG C, slowly Fast 12~36h of stirring reaction, filtering, 80 ~ 90 DEG C of dryings of filter cake obtain V2O5/ PMMA presomas.
（3）, porous V2O5The preparation of/C complex microspheres.By step（2）Middle gained presoma is placed in ceramic crucible, is put into In tube-type atmosphere furnace, 200 DEG C first are warming up to 0.5 DEG C/min speed in air atmosphere, 1h is kept；Lead to nitrogen again after 10 minutes, 350 DEG C are warming up to 0.2 DEG C/min speed, 1h is incubated；It is last that 500 DEG C of sintering 20h are warming up to 0.2 DEG C/min speed, with stove Cool down at a slow speed, synthesizing porous V2O5/ C complex microspheres.Through analysis, porous V2O5Electroactive substance V in/C complex microspheres2O5 Mass fraction be 82%.
By porous V manufactured in the present embodiment2O5/ C complex microspheres, acetylene black and Kynoar are with mass ratio 8.5:0.5:1 It is scattered in 1-METHYLPYRROLIDONE, slurry is stirred at normal temperatures and pressures, be coated uniformly on aluminium foil surface, 120 DEG C is dried in vacuo, A diameter of 1 cm thin rounded flakes are cut into after roll-in, the mg V of average load 3.8 on every plate electrode2O5Electroactive substance. Using it as positive pole, with cathode of lithium and the perforated membranes of Celgard 2300 assembling button cell, electrolyte is 1 mol/L LiPF6's Ethylene carbonate（EC）And dimethyl carbonate（DMC）Solution（Both mass ratioes are 1:1）.
Above-mentioned button cell is tested using constant current charge-discharge technology, test temperature is 25 DEG C, charging termination electricity Press as 4 V, final discharging voltage is 2 V.Respectively with 0.1C, 0.5C, 2C, 5C and 10C（1C=294 mA/g）Discharge and recharge, V2O5Electricity The first discharge specific capacity of chemically reactive substance is respectively 291,264,240,191 and 166 mAh/g；It is respectively with 0.5C, 5C After being circulated 300 times with 10C, specific discharge capacity is respectively 238,147 and 105 mAh/g, and capability retention is respectively 90%, 77% and 63%。
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention. A variety of modifications to these embodiments are it will be apparent that as defined herein one for those skilled in the art As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will It is not constrained to embodiment illustrated herein, but the scope consistent with novelty with principles disclosed herein.

Claims (7)

1. a kind of porous V of positive electrode material of lithium secondary cell2O5The preparation method of/C complex microspheres, it is characterised in that including following step Rapid and method：
Step one, synthesizing cross-linked PMMA microgel balls are polymerize using emulsion method, in deionized water, addition surfactant, Methyl methacrylate MMA monomers and N, N '-methylene-bisacrylamide MBA crosslinking agents, after stirring, are slow added into oxygen Agent solution；After logical nitrogen deoxygenation 1h, the temperature of reaction system is raised to 65~75 DEG C, and condensing reflux 2 under nitrogen protection ~3h, obtains milky mixed liquor；After filtering, gained powder is washed 2~3 times with water and ethanol, and the PMMA being crosslinked is micro- solidifying Glueballs；PMMA microgel balls are reacted into 0.5h in strong alkali solution again, after washing 3 times, room temperature in vacuo dries 24h, is handed over The PMMA microsphere template of connection；
Step 2, changes the pH value in adsorption liquid, VO2+Hydrolysis generation V2O5Nano particle in situ is filled in three-dimensional mesh, is obtained V2O5/ PMMA presomas：In oxalic acid (H2C2O4) solution in, add ammonium metavanadate NH4VO3, it is sufficiently stirred for dissolving；Then add PMMA microsphere template obtained by step one；At 60~80 DEG C, low rate mixing reacts 12~36h, filtering, 80~90 DEG C of perseverances of filter cake Temperature is dried, and obtains V2O5/ PMMA presomas；
V is calcined in step 3, inert atmosphere2O5/ PMMA presomas, make the PMMA strands in presoma be carbonized, obtain porous V2O5/ C complex microspheres：Gained presoma in step 2 is placed in ceramic crucible, is put into tube-type atmosphere furnace, leads to after nitrogen, slowly Speed heating calcine by steps, and cooled down at a slow speed with stove, synthesizing porous V2O5/ C complex microspheres.
2. the porous V of positive electrode material of lithium secondary cell as claimed in claim 12O5The preparation method of/C complex microspheres, its feature exists In the methyl methacrylate and N, N '-methylene-bisacrylamide are (20~30) in mass ratio：1；Ammonium metavanadate and grass The mol ratio of acid is 1：(1.2~1.5)；
The oxidant is the one or more in potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate, and oxidant concentration is 0.1mol/L, consumption is the 20%~50% of MMA monomer molar amounts,
The strong alkali solution be lithium hydroxide, NaOH and potassium hydroxide in one or more, concentration be 0.05~ 0.2mol/L；The concentration of oxalic acid is 0.4~0.6mol/L.
3. the porous V of positive electrode material of lithium secondary cell as claimed in claim 22O5The preparation method of/C complex microspheres, its feature exists In the methyl methacrylate and N, N '-methylene-bisacrylamide are 25 in mass ratio：1；Ammonium metavanadate and oxalic acid rub You are than being 1：1.3.
4. the porous V of positive electrode material of lithium secondary cell as claimed in claim 22O5The preparation method of/C complex microspheres, its feature exists In the oxidizer is the 30% of MMA monomer molar amounts.
5. the porous V of positive electrode material of lithium secondary cell as claimed in claim 12O5The preparation method of/C complex microspheres, its feature exists In surfactant is dodecyl sodium sulfate, sodium cetanesulfonate, neopelex and 18 hard fatty acids sodium In one or more, addition be liquor capacity 0.05~0.1g/L.
6. the porous V of positive electrode material of lithium secondary cell as claimed in claim 22O5The preparation method of/C complex microspheres, its feature exists In strong alkali solution concentration is 0.1mol/L.
7. the porous V of positive electrode material of lithium secondary cell as claimed in claim 22O5The preparation method of/C complex microspheres, its feature exists In concentration of oxalic acid is 0.5mol/L.
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