CN103887495B - Three-dimensional porous classification carbon modifies phosphoric acid vanadium lithium nano material and its preparation method and application - Google Patents

Three-dimensional porous classification carbon modifies phosphoric acid vanadium lithium nano material and its preparation method and application Download PDF

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CN103887495B
CN103887495B CN201410110084.4A CN201410110084A CN103887495B CN 103887495 B CN103887495 B CN 103887495B CN 201410110084 A CN201410110084 A CN 201410110084A CN 103887495 B CN103887495 B CN 103887495B
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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 present invention relates to three-dimensional porous classification carbon and modify Li 3v 2(PO 4) 3the preparation method of nano material, it has obvious loose structure, and granular size is 10-50 μm, and particle is the Li of 0.2-0.5 μm by many sizes 3v 2(PO 4) 3granule forms, surface is all surrounded by uniform carbon-coating, be interconnected by the carbon nano-particle of 10-20nm between granule, this carbon nano-particle defines three-dimensional carbon net, thus granule is wrapped in three-dimensional carbon net, the invention has the beneficial effects as follows: 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, when it is as anode active material of lithium ion battery, shows the feature that power is high, good cycling stability, high temperature performance are good; Secondly, present invention process is simple, and feasibility is strong, is easy to amplificationization, meets the feature of Green Chemistry, is beneficial to the marketization and promotes.

Description

Three-dimensional porous classification carbon modifies 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 to promote the fast development in electric automobile field further, study one of forward position and focus that and low cost lithium ion battery good based on the high power capacity of novel nano structure, high power, high stability, thermal adaptability is current low-carbon economy epoch Study on Li-ion batteries.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 most potentiality.Due to the Li of monoclinic phase 3v 2(PO4) 3for Fast ion conductor structure (NASICON), it can provide the three-dimensional channel for Lithium-ion embeding/deviate from, and thus 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 explore a lot of method to attempt and 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 strategy, 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 significantly can not 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 modified with three-dimensional porous classification carbon 3v 2(PO 4) 3electrode material have not been reported.Therefore, three-dimensional porous classification carbon modifies 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 growth in high-temperature burning process and reunion, also play the effect of resilient coating simultaneously, and the structural deterioration effectively preventing electrode material from causing because of change in volume when Lithium-ion embeding/deviate from, effectively improves the cyclical stability of electrode material.Meanwhile, three-dimensional co-continuous carbon skeleton can significantly improve lithium ion diffusion velocity in the electrodes, reduces its evolving path, thus reduces lithium ion battery polarization under cryogenic, finally realizes Li 3v 2(PO 4) 3electrode material in the application in high power, long-life and high/low temperature electrode material field, thus obtains the potential application material that excellent low temperature becomes 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, only need the concentration changing reactant can control pattern and the size of material, and obtained material yield is high, purity is high, good dispersion.
Summary of the invention
Technical problem to be solved by this invention provides a kind of three-dimensional porous classification carbon to modify Li 3v 2(PO 4) 3/ C and preparation method thereof, its technique is simple, the requirement that meets Green Chemistry and be convenient to amplificationizations, on this basis, three-dimensional porous classification carbon modification Li 3v 2(PO 4) 3also there is excellent chemical property.
The present invention solves the problems of the technologies described above adopted technical scheme: three-dimensional porous classification carbon modifies 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 μm by many sizes 3v 2(PO 4) 3granule forms, Li 3v 2(PO 4) 3granule surface is all surrounded by uniform carbon-coating, Li 3v 2(PO 4) 3be interconnected by the carbon nano-particle of 10-20nm between/C granule, this carbon nano-particle defines three-dimensional carbon net, thus 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, wherein V 2o 5be 1:5-1:7 with the mol ratio of oxalic acid, stirring and dissolving, obtains VOC 2o 4blue solution;
2) measuring with vanadium source mol ratio is the phosphorus source of 1:1.5, is joined the VOC of step 1) gained 2o 4in blue solution, stir;
3) taking with vanadium source mol ratio is the lithium source of 1:1.5, is dissolved in distilled water, is added dropwise to 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, obtain precursor solution;
5) precursor solution is dried at drying box, obtain dark brown solid, solid abrasive is placed in 140-160 DEG C of vacuum drying chamber dry, finally obtains precursor powder;
6) by precursor powder pre-burning in a nitrogen atmosphere, calcine again after pre-burning product is ground a little, 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 modifies 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, wherein V 2o 5be 1:5-1:7 with the mol ratio of oxalic acid, stirring and dissolving, obtains VOC 2o 4blue solution;
2) measuring with vanadium source mol ratio is the phosphorus source of 1:1.5, is joined the VOC of step 1) gained 2o 4in blue solution, stir;
3) taking with vanadium source mol ratio is the lithium source of 1:1.5, is dissolved in distilled water, is added dropwise to 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, obtain precursor solution;
5) precursor solution is dried at drying box, obtain dark brown solid, solid abrasive is placed in 140-160 DEG C of vacuum drying chamber dry, finally obtains precursor powder;
6) by precursor powder pre-burning in a nitrogen atmosphere, calcine again after pre-burning product is ground a little, finally obtain the three-dimensional porous classification carbon of black and modify Li 3v 2(PO 4) 3nano material.
By such scheme, step 2) described in phosphorus source be H 3pO 4and NH 4h 2pO 4in the mixing of any one or they.
By such scheme, the lithium source described in step 3) is LiAc, Li 2cO 3, LiNO 3with the mixing of any one or they in LiCl.
By 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 modifies 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 mainly 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, when it is as anode active material of lithium ion battery, shows the feature that power is high, good cycling stability, high temperature performance are good; Secondly, present invention process is simple, can obtain precursor solution by simple stirring, and under carrying out drying and inert atmosphere to solution, 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.
Accompanying drawing explanation
Fig. 1 is that the three-dimensional porous classification carbon of the embodiment of the present invention 1 modifies 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 modifies 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 modifies 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 modifies 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 modifies 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 modifies 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 modifies Li 3v 2(PO 4) 3the alternating temperature cycle performance of battery figure of nano material.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further 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 modifies 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 5with the mol ratio 1:6 of oxalic acid), at 80 DEG C, mix and blend 10 minutes, obtains VOC 2o 4blue solution;
2) measuring with vanadium source mol ratio is the 85% phosphoric acid (H of 1:1.5 3pO 4) solution (0.716mL), phosphoric acid is dropwise added dropwise in the blue solution of step 1) gained, stirs;
3) take 1.125g Lithium acetate dihydrate (LiAc, lithium source actual amount is 1.05 times of required reacting dose) powder, be dissolved in 5mL distilled water, after dissolving, be added dropwise to step 2) in the blue solution of gained;
4) glucose (C is taken 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 dark brown solid, solid abrasive is placed on dry 8h in 140 DEG C of vacuum drying chambers, finally obtains precursor powder;
6) by precursor powder pre-burning 5h under 350 DEG C of nitrogen atmospheres, after being ground a little by pre-burning product, under 800 DEG C of nitrogen atmospheres, calcine 8h again, finally obtain the continuous Li of the three-dimensional porous binary channels of black 3v 2(PO 4) 3nano material.
Li is modified 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 modifies 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 in sample that contained carbon graphite degree is higher, but due to graphitized carbon be not the structure of long-range order, but to 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 prepared by us 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 μm, short grained Surface coating one deck uniform carbon-coating, and these granules are assembled by the accumulation between particle becomes the bulky grain being of a size of tens microns.Have obvious space between particle, many carbon granules are filled in space, by the Li of dispersion 3v 2(PO 4) 3/ C granule couples together.
Three-dimensional porous classification carbon prepared by the present invention modifies 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 fully being mixed in proportion, add a small amount of isopropyl alcohol, grinding evenly, twin rollers is pressed the electrode slice that about 0.5mm is thick; It is for subsequent use after 24 hours that the positive plate pressed is placed in the oven drying of 80 DEG C.With the LiPF of 1M 6be dissolved in as electrolyte in vinyl carbonate (EC) and dimethyl carbonate (DMC), 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.
Li is modified with the three-dimensional porous classification carbon of the present embodiment gained 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 modifies Li 3v 2(PO 4) 3first discharge specific capacity can reach 126,124,122 and 121mAh/g respectively.The high rate performance excellence (Fig. 5 b) of material, after the discharge and recharge under the different current density of experience 0.5C ~ 20C, the discharge capacity of material under 30C current density still can reach 118.2mAh/g.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, the cyclical stability of material is very outstanding (Fig. 5 c) also, and under the current density of 20C, the specific capacity after material circulation 4000 times is still 94mAh/g, and secondary capacity attenuation rate is only 0.0065%.Meanwhile, we also characterize the performance of sample under high/low temperature condition.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.After probe temperature is reduced to-20 DEG C, the first discharge specific capacity of material still can reach 106.2mAh/g(Fig. 7, and 1C charging/5C discharges), after 450 circulations, capability retention still can reach 87.6%.Subsequently, probe temperature is set in 25 DEG C, the specific discharge capacity of material can rapidly increase to 117.3mAh/g(5C charging/5C and discharge).When temperature is increased to 60 DEG C, the specific capacity of sample is also increased to 125.1mAh/g further.Even if experienced by from the test-20 DEG C of-60 DEG C of different temperatures, when after temperature return to room temperature, the specific discharge capacity of material still can reach 108.3mAh/g.Above-mentioned performance shows, three-dimensional porous classification carbon modifies 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 modifies 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 5with the mol ratio 1:5 of oxalic acid), at 80 DEG C, mix and blend 10 minutes, obtains VOC 2o 4blue solution;
2) measuring with vanadium source mol ratio is the 1.209g ammonium dihydrogen phosphate (NH of 1:1.5 4h 2pO 4) powder, be dropwise added dropwise to after being dissolved in distilled water in the blue solution of step 1) gained, stir;
3) 0.406g lithium carbonate (Li is taken 2cO 3, lithium source actual amount is 1.05 times of required reacting dose) and powder, be dissolved in 5mL distilled water, after dissolving, be added dropwise to step 2) in the blue solution of gained;
4) glucose (C is taken 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 dark brown solid, solid abrasive is placed on dry 8h in 140 DEG C of vacuum drying chambers, finally obtains precursor powder;
6) by precursor powder pre-burning 5h under 350 DEG C of nitrogen atmospheres, after being ground a little by pre-burning product, under 750 DEG C of nitrogen atmospheres, calcine 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 116mAh/g respectively, and after 300 circulations, specific discharge capacity is 106.2mAh/g, and capability retention is 91.5%.
Embodiment 3:
Three-dimensional porous classification carbon modifies 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 5with the mol ratio 1:7 of oxalic acid), at 80 DEG C, mix and blend 10 minutes, obtains VOC 2o 4blue solution;
2) measuring with vanadium source mol ratio is the 85% phosphoric acid (H of 1:1.5 3pO 4) solution (0.716mL), phosphoric acid is dropwise added dropwise in the blue solution of step 1) gained, stirs;
3) 0.406g lithium carbonate (Li is taken 2cO 3, lithium source actual amount is 1.05 times of required reacting dose) and powder, be dissolved in 5mL distilled water, after dissolving, be added dropwise to step 2) in the blue solution of gained;
4) glucose (C is taken 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 dark brown solid, solid abrasive is placed on dry 8h in 160 DEG C of vacuum drying chambers, finally obtains precursor powder;
6) by precursor powder pre-burning 5h under 350 DEG C of nitrogen atmospheres, after being ground a little by pre-burning product, under 850 DEG C of nitrogen atmospheres, calcine 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 117.3mAh/g respectively, and after 300 circulations, specific discharge capacity is 103.3mAh/g, and capability retention is 88%.
Embodiment 4:
Three-dimensional porous classification carbon modifies 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 5with the mol ratio 1:5 of oxalic acid), at 80 DEG C, mix and blend 10 minutes, obtains VOC 2o 4blue solution;
2) measuring with vanadium source mol ratio is the 85% phosphoric acid (H of 1:1.5 3pO 4) solution (0.716mL), phosphoric acid is dropwise added dropwise in the blue solution of step 1) gained, stirs;
3) take 0.466g lithium chloride (LiCl, lithium source actual amount is 1.05 times of required reacting dose) powder, be dissolved in 5mL distilled water, after dissolving, be added dropwise to step 2) in the blue solution of gained;
4) glucose (C is taken 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 dark brown solid, solid abrasive is placed on dry 8h in 140 DEG C of vacuum drying chambers, finally obtains precursor powder;
6) by precursor powder pre-burning 5h under 350 DEG C of nitrogen atmospheres, after being ground a little by pre-burning product, under 800 DEG C of nitrogen atmospheres, calcine 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 117.5mAh/g respectively, 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 5with the mol ratio 1:7 of oxalic acid), at 80 DEG C, mix and blend 10 minutes, obtains VOC 2o 4blue solution;
2) measuring with vanadium source mol ratio is the 1.209g ammonium dihydrogen phosphate (NH of 1:1.5 4h 2pO 4) powder, be dropwise added dropwise to after being dissolved in distilled water in the blue solution of step 1) gained, stir;
3) take 1.125g Lithium acetate dihydrate (LiAc, lithium source actual amount is 1.05 times of required reacting dose) powder, be dissolved in 5mL distilled water, after dissolving, be added dropwise to step 2) in the blue solution of gained;
4) glucose (C is taken 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 dark brown solid, solid abrasive is placed on dry 8h in 140 DEG C of vacuum drying chambers, finally obtains precursor powder;
6) by precursor powder pre-burning 5h under 350 DEG C of nitrogen atmospheres, after being ground a little by pre-burning product, under 800 DEG C of nitrogen atmospheres, calcine 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 118.1mAh/g respectively, 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 5with the mol ratio 1:6 of oxalic acid), at 80 DEG C, mix and blend 10 minutes, obtains VOC 2o 4blue solution;
2) measuring with vanadium source mol ratio is the 85% phosphoric acid (H of 1:1.5 3pO 4) solution (0.716mL), phosphoric acid is dropwise added dropwise in the blue solution of step 1) gained, stirs;
3) 0.406g lithium carbonate (Li is taken 2cO 3, lithium source actual amount is 1.05 times of required reacting dose) and powder, be dissolved in 5mL distilled water, after dissolving, be added dropwise to step 2) in the blue solution of gained;
4) glucose (C is taken 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 dark brown solid, solid abrasive is placed on dry 8h in 140 DEG C of vacuum drying chambers, finally obtains precursor powder;
6) by precursor powder pre-burning 5h under 350 DEG C of nitrogen atmospheres, after being ground a little by pre-burning product, under 800 DEG C of nitrogen atmospheres, calcine 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 122mAh/g respectively, 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 5with the mol ratio 1:6 of oxalic acid), at 80 DEG C, mix and blend 10 minutes, obtains VOC 2o 4blue solution;
2) measuring with vanadium source mol ratio is the 85% phosphoric acid (H of 1:1.5 3pO 4) solution (0.716mL), phosphoric acid is dropwise added dropwise in the blue solution of step 1) gained, stirs;
3) 0.758g lithium nitrate (LiNO is taken 3, lithium source actual amount is 1.05 times of required reacting dose) and powder, be dissolved in 5mL distilled water, after dissolving, be added dropwise to step 2) in the blue solution of gained;
4) glucose (C is taken 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 dark brown solid, solid abrasive is placed on dry 8h in 140 DEG C of vacuum drying chambers, finally obtains precursor powder;
6) by precursor powder pre-burning 5h under 350 DEG C of nitrogen atmospheres, after being ground a little by pre-burning product, under 750 DEG C of nitrogen atmospheres, calcine 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 120mAh/g respectively, and after 300 circulations, specific discharge capacity is 111mAh/g, and capability retention is 92.5%.

Claims (3)

1. three-dimensional porous classification carbon modifies 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 μm by many sizes 3v 2(PO 4) 3granule forms, Li 3v 2(PO 4) 3granule surface is all surrounded by uniform carbon-coating, Li 3v 2(PO 4) 3be interconnected by the carbon nano-particle of 10-20nm between/C granule, this carbon nano-particle defines three-dimensional carbon net, thus 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, wherein V 2o 5be 1:5-1:7 with the mol ratio of oxalic acid, stirring and dissolving, obtains VOC 2o 4blue solution;
2) measuring with vanadium source mol ratio is the phosphorus source of 1:1.5, is joined step 1) VOC of gained 2o 4in blue solution, stir; Described phosphorus source is H 3pO 4and NH 4h 2pO 4in the mixing of any one or they;
3) taking with vanadium source mol ratio is the lithium source of 1:1.5, is dissolved in distilled water, is added dropwise to step 2 after dissolving) in gained solution;
Described lithium source is LiAc, Li 2cO 3, LiNO 3with the mixing of any one or they in LiCl;
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 step 3) in gained solution, stir, obtain precursor solution;
5) precursor solution is dried at drying box, obtain dark brown solid, solid abrasive is placed in 140-160 DEG C of vacuum drying chamber dry, finally obtains precursor powder;
6) by precursor powder pre-burning in a nitrogen atmosphere, described calcined temperature is 350 DEG C, and the time is 5 hours, and calcining heat is 750-850 DEG C, and the time is 8 hours; Calcine again after pre-burning product is ground a little, 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 according to claim 1 modifies 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, wherein V 2o 5be 1:5-1:7 with the mol ratio of oxalic acid, stirring and dissolving, obtains VOC 2o 4blue solution;
2) measuring with vanadium source mol ratio is the phosphorus source of 1:1.5, is joined step 1) VOC of gained 2o 4in blue solution, stir; Described phosphorus source is H 3pO 4and NH 4h 2pO 4in the mixing of any one or they;
3) taking with vanadium source mol ratio is the lithium source of 1:1.5, is dissolved in distilled water, is added dropwise to step 2 after dissolving) in gained solution;
Described lithium source is LiAc, Li 2cO 3, LiNO 3with the mixing of any one or they in LiCl;
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 step 3) in gained solution, stir, obtain precursor solution;
5) precursor solution is dried at drying box, obtain dark brown solid, solid abrasive is placed in 140-160 DEG C of vacuum drying chamber dry, finally obtains precursor powder;
6) by precursor powder pre-burning in a nitrogen atmosphere, described calcined temperature is 350 DEG C, and the time is 5 hours, and calcining heat is 750-850 DEG C, and the time is 8 hours; Calcine again after pre-burning product is ground a little, finally obtain the three-dimensional porous classification carbon of black and modify Li 3v 2(PO 4) 3nano material.
3. three-dimensional porous classification carbon according to claim 1 modifies the application of phosphoric acid vanadium lithium nano material as anode active material of lithium ion battery.
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