CN103887495A - Lithium vanadium phosphate nanometer material modified by three dimensional porous classification carbon, preparation method and application thereof - Google Patents

Lithium vanadium phosphate nanometer material modified by three dimensional porous classification carbon, preparation method and application thereof Download PDF

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CN103887495A
CN103887495A CN201410110084.4A CN201410110084A CN103887495A CN 103887495 A CN103887495 A CN 103887495A CN 201410110084 A CN201410110084 A CN 201410110084A CN 103887495 A CN103887495 A CN 103887495A
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麦立强
罗艳珠
许絮
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Wuhan University of Technology WUT
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Abstract

The invention relates to a preparation method of a Li3V2(PO4)3 (lithium vanadium phosphate) nanometer material modified by three dimensional porous classification carbon, wherein the Li3V2(PO4)3 nanometer material has an obvious porous structure, the sizes of particles are 10-50 micrometers, and each particle is formed by a plurality of small particles of Li3V2(PO4)3, the size of each small particle is 0.2-0.5 micrometer, the surface of each small particle is wrapped by a uniform carbon layer, and the small particles are connected each other by virtue of carbon nanometer particles of which the size is 10-20 nanometer, the carbon nanometer particles form a three dimensional carbon web, so that the small particles are wrapped in the three dimensional carbon web. The preparation method of the lithium vanadium Li3V2(PO4)3 (lithium vanadium phosphate) nanometer material modified by three dimensional porous classification carbon provided by the invention has the beneficial effects that by virtue of a simple and easy solution method combined with a solid state sintering method, the Li3V2(PO4)3 nanometer material modified by three dimensional porous classification carbon is prepared, and when the Li3V2(PO4)3 nanometer material is used as a positive active material of a lithium battery, the Li3V2(PO4)3 nanometer material has the characteristics of high power, good cycling stability and good high-and-low temperature performance; secondly, the invention is simple in technology, strong in feasibility and easy to amplify, meets the characteristic of green chemistry, and facilitates the market extension.

Description

Three-dimensional porous classification carbon is modified phosphoric acid vanadium lithium nano material and its preparation method and application
Technical field
The invention belongs to nano material and technical field of electrochemistry, be specifically related to three-dimensional porous classification carbon and modify Li 3v 2(PO 4) 3the preparation method of nano material, this material can be used as anode active material of lithium ion battery.
Background technology
Nowadays, in order further to promote the fast development in electric automobile field, the good and low cost lithium ion battery of high power capacity, high power, high stability, the thermal adaptability of research based on novel nano structure is one of the forward position of current low-carbon economy epoch Study on Li-ion batteries using and focus.Li 3v 2(PO4) 3have that structural stability is good, current potential is high, thermally-stabilised good and capacity is high, be considered to one of anode material for lithium-ion batteries of tool potentiality.Due to the Li of monoclinic phase 3v 2(PO4) 3for sodium fast-ionic conductor structure (NASICON), it can provide the three-dimensional channel that embeds/deviate from for lithium ion, thereby has high lithium ion diffusion coefficient (10 -9～10 -10cm 2s -1).But, Li 3v 2(PO 4) 3electronic conductivity lower, finally limit its application as high power electrodes material.
In recent years, researchers have explored a lot of methods and have attempted to solve Li 3v 2(PO 4) 3the shortcoming that electronic conductivity is low, comprises that carbon is coated, the mode such as nanometer and doping.In numerous strategies, carbon is coated is a kind of both economical and method easily.But, to Li 3v 2(PO 4) 3carry out the coated electronic conductivity that can not significantly improve electrode material of simple carbon.Three-dimensional co-continuous passage carbon skeleton can provide the duplicate transmissions passage of electronics and ion, reduces the transmission path of ion, and improves the contact area of electrolyte and electrode material.But, the Li modifying with three-dimensional porous classification carbon 3v 2(PO 4) 3electrode material have not been reported.Therefore, three-dimensional porous classification carbon is modified Li 3v 2(PO 4) 3electrode material has that specific area is large, electric charge mass transfer resistance is low and electronic conductivity improves obvious advantage.In addition Li, 3v 2(PO 4) 3carbon net between particle can limit Li 3v 2(PO 4) 3particle in high-temperature calcination process is grown up and is reunited, and also plays the effect of resilient coating simultaneously, effectively prevents the structural deterioration that electrode material causes because of change in volume in the time that lithium ion embeds/deviates from, and effectively improves the cyclical stability of electrode material.Meanwhile, three-dimensional co-continuous carbon skeleton can significantly improve the diffusion velocity of lithium ion in electrode, reduces its evolving path, thereby reduces the polarization of lithium ion battery under cryogenic conditions, finally realizes Li 3v 2(PO 4) 3electrode material is in the application in high power, long-life and high low temperature electrode material field, thereby obtains excellent low temperature and become the potential application material of lithium ion battery.
In addition, prepare three-dimensional porous classification carbon and modify Li 3v 2(PO 4) 3the solwution method that nano material adopts is simple, does not need to add other organic substances, and the concentration that only need to change reactant can be controlled pattern and the size of material, and the material yield making is high, purity is high, good dispersion.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of three-dimensional porous classification carbon to modify Li for above-mentioned prior art 3v 2(PO 4) 3/ C and preparation method thereof, its technique is simple, meet the requirement of Green Chemistry and be convenient to amplificationizations, on this basis, three-dimensional porous classification carbon modification Li 3v 2(PO 4) 3also there is good chemical property.
The present invention solves the problems of the technologies described above adopted technical scheme: three-dimensional porous classification carbon is modified phosphoric acid vanadium lithium nano material, and it has obvious loose structure, and granular size is 10-50 μm, and particle is the Li of 0.2-0.5 μ m by many sizes 3v 2(PO 4) 3granule composition, Li 3v 2(PO 4) 3granule surface is all surrounded by uniform carbon-coating, Li 3v 2(PO 4) 3between/C granule, interconnected by the carbon nano-particle of 10-20nm, this carbon nano-particle has formed three-dimensional carbon net, thereby by Li 3v 2(PO 4) 3granule is wrapped in three-dimensional carbon net, and it is following method products therefrom, includes following steps:
1) vanadium source vanadic oxide and oxalic acid are joined in distilled water to wherein V 2o 5with the mol ratio of oxalic acid be 1:5-1:7, stirring and dissolving, obtains VOC 2o 4blue solution;
2) the phosphorus source that to measure with vanadium source mol ratio be 1:1.5, is joined the VOC of step 1) gained 2o 4in blue solution, stir;
3) the lithium source that to take with vanadium source mol ratio be 1:1.5, is dissolved in distilled water, splashes into step 2 after dissolving) in gained solution;
4) take glucose as carbon source, wherein the mol ratio of vanadium source and glucose is 2:0.5-2:1.2, is dissolved in distilled water, dropwise joins in step 3) gained solution, stirs, and obtains precursor solution;
5) precursor solution is dried at drying box, obtain pitchy solid, solid abrasive is placed in 140-160 DEG C of vacuum drying chamber and is dried, finally obtain precursor powder;
6) by precursor powder pre-burning under nitrogen atmosphere, after being ground a little, calcines again pre-burning product, and finally obtain the three-dimensional porous classification carbon of black and modify Li 3v 2(PO 4) 3nano material.
Described three-dimensional porous classification carbon is modified the preparation method of phosphoric acid vanadium lithium nano material, includes following steps:
1) vanadium source vanadic oxide and oxalic acid are joined in distilled water to wherein V 2o 5with the mol ratio of oxalic acid be 1:5-1:7, stirring and dissolving, obtains VOC 2o 4blue solution;
2) the phosphorus source that to measure with vanadium source mol ratio be 1:1.5, is joined the VOC of step 1) gained 2o 4in blue solution, stir;
3) the lithium source that to take with vanadium source mol ratio be 1:1.5, is dissolved in distilled water, splashes into step 2 after dissolving) in gained solution;
4) take glucose as carbon source, wherein the mol ratio of vanadium source and glucose is 2:0.5-2:1.2, is dissolved in distilled water, dropwise joins in step 3) gained solution, stirs, and obtains precursor solution;
5) precursor solution is dried at drying box, obtain pitchy solid, solid abrasive is placed in 140-160 DEG C of vacuum drying chamber and is dried, finally obtain precursor powder;
6) by precursor powder pre-burning under nitrogen atmosphere, after being ground a little, calcines again pre-burning product, and finally obtain the three-dimensional porous classification carbon of black and modify Li 3v 2(PO 4) 3nano material.
Press such scheme, step 2) described phosphorus source is H 3pO 4and NH 4h 2pO 4in the mixing of any one or they.
Press such scheme, the lithium source described in step 3) is LiAc, Li 2cO 3, LiNO 3mixing with any one or they in LiCl.
Press such scheme, the calcined temperature described in step 6) is 350 DEG C, and the time is 5 hours, and calcining heat is 750-850 DEG C, and the time is 8 hours.
Described three-dimensional porous classification carbon is modified the application of phosphoric acid vanadium lithium nano material as anode active material of lithium ion battery.
The invention has the beneficial effects as follows: the present invention has prepared in conjunction with solid sintering technology the Li that three-dimensional porous classification carbon is modified by simple solwution method 3v 2(PO 4) 3nano material, it is during as anode active material of lithium ion battery, shows that power is high, good cycling stability, the good feature of high temperature performance; Secondly, technique of the present invention is simple, can obtain precursor solution by simple stirring, to solution be dried and inert atmosphere under solid-phase sintering can obtain three-dimensional porous classification carbon modification Li 3v 2(PO 4) 3nano material.The method feasibility is strong, is easy to amplificationization, meets the feature of Green Chemistry, is beneficial to the marketization and promotes.
Brief description of the drawings
Fig. 1 is that the three-dimensional porous classification carbon of the embodiment of the present invention 1 is modified Li 3v 2(PO 4) 3the XRD figure of nano material;
Fig. 2 is that the three-dimensional porous classification carbon of the embodiment of the present invention 1 is modified Li 3v 2(PO 4) 3the Raman figure of nano material;
Fig. 3 is that the three-dimensional porous classification carbon of the embodiment of the present invention 1 is modified Li 3v 2(PO 4) 3the SEM figure of nano material;
Fig. 4 is that the three-dimensional porous classification carbon of the embodiment of the present invention 1 is modified Li 3v 2(PO 4) 3the TEM figure of nano material;
Fig. 5 is that the three-dimensional porous classification carbon of the embodiment of the present invention 1 is modified Li 3v 2(PO 4) 3the normal temperature cycle performance of battery figure of nano material;
Fig. 6 is that the three-dimensional porous classification carbon of the embodiment of the present invention 1 is modified Li 3v 2(PO 4) 3the high-temperature battery cycle performance figure of nano material;
Fig. 7 is that the three-dimensional porous classification carbon of the embodiment of the present invention 1 is modified Li 3v 2(PO 4) 3the alternating temperature cycle performance of battery figure of nano material.
Embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1:
Three-dimensional porous classification carbon is modified Li 3v 2(PO 4) 3the preparation method of nano material, it comprises the steps:
1) by 0.637g vanadic oxide (V 2o 5) and 2.646g oxalic acid (C 2h 2o 4) join (V in 20mL distilled water 2o 5mol ratio 1:6 with oxalic acid), at 80 DEG C, mix and blend 10 minutes, obtains VOC 2o 4blue solution;
2) the 85% phosphoric acid (H that to measure with vanadium source mol ratio be 1:1.5 3pO 4) solution (0.716mL), phosphoric acid is dropwise splashed in the blue solution of step 1) gained, stir;
3) take 1.125g Lithium acetate dihydrate (LiAc, 1.05 times that lithium source actual amount is required reacting dose) powder, be dissolved in 5mL distilled water, after dissolving, splash into step 2) in the blue solution of gained;
4) take glucose (C 6h 12o 6) mol ratio of powder 0.5g(vanadium source and glucose is 2:0.79), be dissolved in 5mL distilled water, dropwise join in step 3) gained solution, stir 5h, obtain presoma blue solution;
5) precursor solution is dried at 120 DEG C of drying boxes, obtain pitchy solid, solid abrasive is placed on to dry 8h in 140 DEG C of vacuum drying chambers, finally obtain precursor powder;
6) by precursor powder pre-burning 5h under 350 DEG C of nitrogen atmospheres, after being ground a little, pre-burning product under 800 DEG C of nitrogen atmospheres, calcines 8h again, finally obtain the continuous Li of the three-dimensional porous binary channels of black 3v 2(PO 4) 3nano material.
Modify Li with the three-dimensional porous classification carbon of product of the present invention 3v 2(PO 4) 3nano material is example, and its structure is determined by x-ray diffractometer and Raman spectrometer.As shown in Figure 1, X-ray diffracting spectrum (XRD) shows, three-dimensional porous classification carbon modification Li 3v 2(PO 4) 3thing phase and card number are the Li of 01-072-7074 3v 2(PO 4) 3standard sample fits like a glove, and sample is monocline, and space group is P2 1/ n, without dephasign peak and C peak.Although the I of Raman energy spectrum (Fig. 2) d/ I gbe 0.98, show that carbon graphite degree contained in sample is higher, but because graphitized carbon is not the structure of long-range order, but be dispersed in agraphitic carbon, so XRD can not detect the peak of crystallization graphite.
SEM image (Fig. 3) and TEM image (Fig. 4) show the Li that we are prepared 3v 2(PO 4) 3/ C is three-dimensional porous hierarchy.Independent Li 3v 2(PO 4) 3/ C granular size is 0.2-0.5 μ m, and short grained surface has been coated the uniform carbon-coating of one deck, and these granules are assembled and become the bulky grain that is of a size of tens microns by the accumulation between particle.Between particle, have obvious space, many carbon granules are filled in space, by the Li disperseing 3v 2(PO 4) 3/ C granule couples together.
Three-dimensional porous classification carbon prepared by the present invention is modified Li 3v 2(PO 4) 3as anode active material of lithium ion battery, all the other steps of the preparation method of lithium ion battery are identical with common preparation method.The preparation method of positive plate is as follows, adopts three-dimensional porous classification carbon to modify Li 3v 2(PO 4) 3as active material, acetylene black is as conductive agent, and polytetrafluoroethylene is as binding agent, and the mass ratio of active material, acetylene black, polytetrafluoroethylene is 70:20:10; After they are fully mixed in proportion, add a small amount of isopropyl alcohol, grind evenly, on twin rollers, press the electrode slice that about 0.5mm is thick; It is for subsequent use after 24 hours that the positive plate pressing is placed in the oven drying of 80 DEG C.With the LiPF of 1M 6be dissolved in vinyl carbonate (EC) and dimethyl carbonate (DMC) as electrolyte, lithium sheet is negative pole, and Celgard2325 is barrier film, and CR2025 type stainless steel is that battery case is assembled into fastening lithium ionic cell.
Three-dimensional porous classification carbon with the present embodiment gained is modified Li 3v 2(PO 4) 3for example, as shown in Figure 5 a, under the current density of 1C, 5C, 20C and 30C, three-dimensional porous classification carbon is modified Li 3v 2(PO 4) 3first discharge specific capacity can reach respectively 126,124,122 and 121mAh/g.(Fig. 5 b),, after discharging and recharging under the different current densities of experience 0.5C～20C, the discharge capacity of material under 30C current density still can reach 118.2mAh/g for the high rate performance excellence of material.After the above-mentioned fast charging and discharging of experience, the capacity of material under 1C current density can return to 120.5mAh/g, and the structural stability of illustrative material is good.In addition, also very outstanding (Fig. 5 c), under the current density of 20C, the specific capacity after material circulation 4000 times is still 94mAh/g to the cyclical stability of material, and inferior capacity attenuation rate is only 0.0065%.Meanwhile, we also characterize in the performance under high/low temperature condition sample.Under 60 DEG C of test conditions (Fig. 6), the specific discharge capacity of sample under 5C and 20C current density is respectively 132.1 and 130.1mAh/g.Circulate after 1000 times, the capability retention of material under 20C current density is 85%, and this shows that material structure is at high temperature highly stable.Probe temperature is reduced to after-20 DEG C, the first discharge specific capacity of material still can reach 106.2mAh/g(Fig. 7,1C charging/5C electric discharge), after 450 circulations, capability retention still can reach 87.6%.Subsequently, probe temperature is set in to 25 DEG C, the specific discharge capacity of material can rapidly increase to 117.3mAh/g(5C charging/5C electric discharge).When temperature is increased to 60 DEG C, the specific capacity of sample is also further increased to 125.1mAh/g.Even if experienced the test from-20 DEG C of-60 DEG C of different temperatures, when temperature returns to after room temperature, the specific discharge capacity of material still can reach 108.3mAh/g.Above-mentioned performance shows, three-dimensional porous classification carbon modification Li 3v 2(PO 4) 3having very excellent chemical property, is a kind of potential anode material for lithium-ion batteries.
Embodiment 2:
Three-dimensional porous classification carbon is modified Li 3v 2(PO 4) 3the preparation method of nano material, it comprises the steps:
1) by 0.637g vanadic oxide (V 2o 5) and 2.205g oxalic acid (C 2h 2o 4) join (V in 20mL distilled water 2o 5mol ratio 1:5 with oxalic acid), at 80 DEG C, mix and blend 10 minutes, obtains VOC 2o 4blue solution;
2) the 1.209g ammonium dihydrogen phosphate (NH that to measure with vanadium source mol ratio be 1:1.5 4h 2pO 4) powder, dropwise splash in the blue solution of step 1) gained after being dissolved in distilled water, stir;
3) take 0.406g lithium carbonate (Li 2cO 3, lithium source actual amount is required reacting dose 1.05 times) powder, be dissolved in 5mL distilled water, after dissolving, splash into step 2) in the blue solution of gained;
4) take glucose (C 6h 12o 6) mol ratio of powder 0.631g(vanadium source and glucose is 2:1), be dissolved in 5mL distilled water, dropwise join in step 3) gained solution, stir 5h, obtain presoma blue solution;
5) precursor solution is dried at 120 DEG C of drying boxes, obtain pitchy solid, solid abrasive is placed on to dry 8h in 140 DEG C of vacuum drying chambers, finally obtain precursor powder;
6) by precursor powder pre-burning 5h under 350 DEG C of nitrogen atmospheres, after being ground a little, pre-burning product under 750 DEG C of nitrogen atmospheres, calcines 8h again, finally obtain the continuous Li of the three-dimensional porous binary channels of black 3v 2(PO 4) 3nano material.
With the Li of the present embodiment gained 3v 2(PO 4) 3/ C is example, under 5C current density, and Li 3v 2(PO 4) 3the first discharge specific capacity of/C can reach respectively 116mAh/g, and after 300 circulations, specific discharge capacity is 106.2mAh/g, and capability retention is 91.5%.
Embodiment 3:
Three-dimensional porous classification carbon is modified Li 3v 2(PO 4) 3the preparation method of nano material, it comprises the steps:
1) by 0.637g vanadic oxide (V 2o 5) and 3.087g oxalic acid (C 2h 2o 4) join (V in 20mL distilled water 2o 5mol ratio 1:7 with oxalic acid), at 80 DEG C, mix and blend 10 minutes, obtains VOC 2o 4blue solution;
2) the 85% phosphoric acid (H that to measure with vanadium source mol ratio be 1:1.5 3pO 4) solution (0.716mL), phosphoric acid is dropwise splashed in the blue solution of step 1) gained, stir;
3) take 0.406g lithium carbonate (Li 2cO 3, lithium source actual amount is required reacting dose 1.05 times) powder, be dissolved in 5mL distilled water, after dissolving, splash into step 2) in the blue solution of gained;
4) take glucose (C 6h 12o 6) mol ratio of powder 0.315g(vanadium source and glucose is 2:0.5), be dissolved in 5mL distilled water, dropwise join in step 3) gained solution, stir 5h, obtain presoma blue solution;
5) precursor solution is dried at 120 DEG C of drying boxes, obtain pitchy solid, solid abrasive is placed on to dry 8h in 160 DEG C of vacuum drying chambers, finally obtain precursor powder;
6) by precursor powder pre-burning 5h under 350 DEG C of nitrogen atmospheres, after being ground a little, pre-burning product under 850 DEG C of nitrogen atmospheres, calcines 8h again, finally obtain the continuous Li of the three-dimensional porous binary channels of black 3v 2(PO 4) 3nano material.
With the Li of the present embodiment gained 3v 2(PO 4) 3/ C is example, under 5C current density, and Li 3v 2(PO 4) 3the first discharge specific capacity of/C can reach respectively 117.3mAh/g, and after 300 circulations, specific discharge capacity is 103.3mAh/g, and capability retention is 88%.
Embodiment 4:
Three-dimensional porous classification carbon is modified Li 3v 2(PO 4) 3the preparation method of nano material, it comprises the steps:
1) by 0.637g vanadic oxide (V 2o 5) and 2.205g oxalic acid (C 2h 2o 4) join (V in 20mL distilled water 2o 5mol ratio 1:5 with oxalic acid), at 80 DEG C, mix and blend 10 minutes, obtains VOC 2o 4blue solution;
2) the 85% phosphoric acid (H that to measure with vanadium source mol ratio be 1:1.5 3pO 4) solution (0.716mL), phosphoric acid is dropwise splashed in the blue solution of step 1) gained, stir;
3) take 0.466g lithium chloride (LiCl, 1.05 times that lithium source actual amount is required reacting dose) powder, be dissolved in 5mL distilled water, after dissolving, splash into step 2) in the blue solution of gained;
4) take glucose (C 6h 12o 6) mol ratio of powder 0.757g(vanadium source and glucose is 2:1.2), be dissolved in 5mL distilled water, dropwise join in step 3) gained solution, stir 5h, obtain presoma blue solution;
5) precursor solution is dried at 120 DEG C of drying boxes, obtain pitchy solid, solid abrasive is placed on to dry 8h in 140 DEG C of vacuum drying chambers, finally obtain precursor powder;
6) by precursor powder pre-burning 5h under 350 DEG C of nitrogen atmospheres, after being ground a little, pre-burning product under 800 DEG C of nitrogen atmospheres, calcines 8h again, finally obtain the continuous Li of the three-dimensional porous binary channels of black 3v 2(PO 4) 3nano material.
With the Li of the present embodiment gained 3v 2(PO 4) 3/ C is example, under 5C current density, and Li 3v 2(PO 4) 3the first discharge specific capacity of/C can reach respectively 117.5mAh/g, and after 300 circulations, specific discharge capacity is 110.3mAh/g, and capability retention is 93.9%.
Embodiment 5:
Three-dimensional co-continuous passage Li 3v 2(PO 4) 3the preparation method of nano material, it comprises the steps:
1) by 0.637g vanadic oxide (V 2o 5) and 3.087g oxalic acid (C 2h 2o 4) join (V in 20mL distilled water 2o 5mol ratio 1:7 with oxalic acid), at 80 DEG C, mix and blend 10 minutes, obtains VOC 2o 4blue solution;
2) the 1.209g ammonium dihydrogen phosphate (NH that to measure with vanadium source mol ratio be 1:1.5 4h 2pO 4) powder, dropwise splash in the blue solution of step 1) gained after being dissolved in distilled water, stir;
3) take 1.125g Lithium acetate dihydrate (LiAc, 1.05 times that lithium source actual amount is required reacting dose) powder, be dissolved in 5mL distilled water, after dissolving, splash into step 2) in the blue solution of gained;
4) take glucose (C 6h 12o 6) mol ratio of powder 0.442g(vanadium source and glucose is 2:0.7), be dissolved in 5mL distilled water, dropwise join in step 3) gained solution, stir 5h, obtain presoma blue solution;
5) precursor solution is dried at 120 DEG C of drying boxes, obtain pitchy solid, solid abrasive is placed on to dry 8h in 140 DEG C of vacuum drying chambers, finally obtain precursor powder;
6) by precursor powder pre-burning 5h under 350 DEG C of nitrogen atmospheres, after being ground a little, pre-burning product under 800 DEG C of nitrogen atmospheres, calcines 8h again, finally obtain the continuous Li of the three-dimensional porous binary channels of black 3v 2(PO 4) 3nano material.
With the Li of the present embodiment gained 3v 2(PO 4) 3/ C is example, under 5C current density, and Li 3v 2(PO 4) 3the first discharge specific capacity of/C can reach respectively 118.1mAh/g, and after 300 circulations, specific discharge capacity is 105.9mAh/g, and capability retention is 89.7%.
Embodiment 6:
Three-dimensional co-continuous passage Li 3v 2(PO 4) 3the preparation method of nano material, it comprises the steps:
1) by 0.637g vanadic oxide (V 2o 5) and 2.646g oxalic acid (C 2h 2o 4) join (V in 20mL distilled water 2o 5mol ratio 1:6 with oxalic acid), at 80 DEG C, mix and blend 10 minutes, obtains VOC 2o 4blue solution;
2) the 85% phosphoric acid (H that to measure with vanadium source mol ratio be 1:1.5 3pO 4) solution (0.716mL), phosphoric acid is dropwise splashed in the blue solution of step 1) gained, stir;
3) take 0.406g lithium carbonate (Li 2cO 3, lithium source actual amount is required reacting dose 1.05 times) powder, be dissolved in 5mL distilled water, after dissolving, splash into step 2) in the blue solution of gained;
4) take glucose (C 6h 12o 6) mol ratio of powder 0.757g(vanadium source and glucose is 2:1.2), be dissolved in 5mL distilled water, dropwise join in step 3) gained solution, stir 5h, obtain presoma blue solution;
5) precursor solution is dried at 120 DEG C of drying boxes, obtain pitchy solid, solid abrasive is placed on to dry 8h in 140 DEG C of vacuum drying chambers, finally obtain precursor powder;
6) by precursor powder pre-burning 5h under 350 DEG C of nitrogen atmospheres, after being ground a little, pre-burning product under 800 DEG C of nitrogen atmospheres, calcines 8h again, finally obtain the continuous Li of the three-dimensional porous binary channels of black 3v 2(PO 4) 3nano material.
With the Li of the present embodiment gained 3v 2(PO 4) 3/ C is example, under 5C current density, and Li 3v 2(PO 4) 3the first discharge specific capacity of/C can reach respectively 122mAh/g, and after 300 circulations, specific discharge capacity is 115mAh/g, and capability retention is 94.3%.
Embodiment 7:
Three-dimensional co-continuous passage Li 3v 2(PO 4) 3the preparation method of nano material, it comprises the steps:
1) by 0.637g vanadic oxide (V 2o 5) and 2.646g oxalic acid (C 2h 2o 4) join (V in 20mL distilled water 2o 5mol ratio 1:6 with oxalic acid), at 80 DEG C, mix and blend 10 minutes, obtains VOC 2o 4blue solution;
2) the 85% phosphoric acid (H that to measure with vanadium source mol ratio be 1:1.5 3pO 4) solution (0.716mL), phosphoric acid is dropwise splashed in the blue solution of step 1) gained, stir;
3) take 0.758g lithium nitrate (LiNO 3, lithium source actual amount is required reacting dose 1.05 times) powder, be dissolved in 5mL distilled water, after dissolving, splash into step 2) in the blue solution of gained;
4) take glucose (C 6h 12o 6) mol ratio of powder 0.442g(vanadium source and glucose is 2:0.7), be dissolved in 5mL distilled water, dropwise join in step 3) gained solution, stir 5h, obtain presoma blue solution;
5) precursor solution is dried at 120 DEG C of drying boxes, obtain pitchy solid, solid abrasive is placed on to dry 8h in 140 DEG C of vacuum drying chambers, finally obtain precursor powder;
6) by precursor powder pre-burning 5h under 350 DEG C of nitrogen atmospheres, after being ground a little, pre-burning product under 750 DEG C of nitrogen atmospheres, calcines 8h again, finally obtain the continuous Li of the three-dimensional porous binary channels of black 3v 2(PO 4) 3nano material.
With the Li of the present embodiment gained 3v 2(PO 4) 3/ C is example, under 5C current density, and Li 3v 2(PO 4) 3the first discharge specific capacity of/C can reach respectively 120mAh/g, and after 300 circulations, specific discharge capacity is 111mAh/g, and capability retention is 92.5%.

Claims (9)

1. three-dimensional porous classification carbon is modified phosphoric acid vanadium lithium nano material, and it has obvious loose structure, and granular size is 10-50 μ m, and particle is the Li of 0.2-0.5 μ m by many sizes 3v 2(PO 4) 3granule composition, Li 3v 2(PO 4) 3granule surface is all surrounded by uniform carbon-coating, Li 3v 2(PO 4) 3between/C granule, interconnected by the carbon nano-particle of 10-20nm, this carbon nano-particle has formed three-dimensional carbon net, thereby by Li 3v 2(PO 4) 3granule is wrapped in three-dimensional carbon net, and it is following method products therefrom, includes following steps:
1) vanadium source vanadic oxide and oxalic acid are joined in distilled water to wherein V 2o 5with the mol ratio of oxalic acid be 1:5-1:7, stirring and dissolving, obtains VOC 2o 4blue solution;
2) the phosphorus source that to measure with vanadium source mol ratio be 1:1.5, is joined the VOC of step 1) gained 2o 4in blue solution, stir;
3) the lithium source that to take with vanadium source mol ratio be 1:1.5, is dissolved in distilled water, splashes into step 2 after dissolving) in gained solution;
4) take glucose as carbon source, wherein the mol ratio of vanadium source and glucose is 2:0.5-2:1.2, is dissolved in distilled water, dropwise joins in step 3) gained solution, stirs, and obtains precursor solution;
5) precursor solution is dried at drying box, obtain pitchy solid, solid abrasive is placed in 140-160 DEG C of vacuum drying chamber and is dried, finally obtain precursor powder;
6) by precursor powder pre-burning under nitrogen atmosphere, after being ground a little, calcines again pre-burning product, and finally obtain the three-dimensional porous classification carbon of black and modify Li 3v 2(PO 4) 3nano material.
2. three-dimensional porous classification carbon as claimed in claim 1 is modified phosphoric acid vanadium lithium nano material, it is characterized in that step 2) described phosphorus source is H 3pO 4and NH 4h 2pO 4in the mixing of any one or they.
3. three-dimensional porous classification carbon as claimed in claim 1 is modified phosphoric acid vanadium lithium nano material, it is characterized in that, the lithium source described in step 3) is LiAc, Li 2cO 3, LiNO 3mixing with any one or they in LiCl.
4. three-dimensional porous classification carbon as claimed in claim 1 is modified phosphoric acid vanadium lithium nano material, it is characterized in that, the calcined temperature described in step 6) is 350 DEG C, and the time is 5 hours, and calcining heat is 750-850 DEG C, and the time is 8 hours.
5. three-dimensional porous classification carbon claimed in claim 1 is modified the preparation method of phosphoric acid vanadium lithium nano material, includes following steps:
1) vanadium source vanadic oxide and oxalic acid are joined in distilled water to wherein V 2o 5with the mol ratio of oxalic acid be 1:5-1:7, stirring and dissolving, obtains VOC 2o 4blue solution;
2) the phosphorus source that to measure with vanadium source mol ratio be 1:1.5, is joined the VOC of step 1) gained 2o 4in blue solution, stir;
3) the lithium source that to take with vanadium source mol ratio be 1:1.5, is dissolved in distilled water, splashes into step 2 after dissolving) in gained solution;
4) take glucose as carbon source, wherein the mol ratio of vanadium source and glucose is 2:0.5-2:1.2, is dissolved in distilled water, dropwise joins in step 3) gained solution, stirs, and obtains precursor solution;
5) precursor solution is dried at drying box, obtain pitchy solid, solid abrasive is placed in 140-160 DEG C of vacuum drying chamber and is dried, finally obtain precursor powder;
6) by precursor powder pre-burning under nitrogen atmosphere, after being ground a little, calcines again pre-burning product, and finally obtain the three-dimensional porous classification carbon of black and modify Li 3v 2(PO 4) 3nano material.
6. three-dimensional porous classification carbon as claimed in claim 5 is modified phosphoric acid vanadium lithium nano material, it is characterized in that step 2) described phosphorus source is H 3pO 4and NH 4h 2pO 4in the mixing of any one or they.
7. three-dimensional porous classification carbon as claimed in claim 5 is modified the preparation method of phosphoric acid vanadium lithium nano material, it is characterized in that, the lithium source described in step 3) is LiAc, Li 2cO 3, LiNO 3mixing with any one or they in LiCl.
8. three-dimensional porous classification carbon as claimed in claim 5 is modified the preparation method of phosphoric acid vanadium lithium nano material, it is characterized in that, the calcined temperature described in step 6) is 350 DEG C, and the time is 5 hours, and calcining heat is 750-850 DEG C, and the time is 8 hours.
9. three-dimensional porous classification carbon claimed in claim 1 is modified the application of phosphoric acid vanadium lithium nano material as anode active material of lithium ion battery.
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CN104134799A (en) * 2014-08-15 2014-11-05 武汉理工力强能源有限公司 Carbon-decorated porous lithium vanadium phosphate nanosphere material as well as preparation method and application thereof
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CN106450307A (en) * 2016-12-16 2017-02-22 武汉理工力强能源有限公司 Graded inner connection carbon modification Na3V2(PO4)3 (vanadium sodium phosphate) electrode material, and preparation method and application thereof
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