CN102509792A - Biomimetic synthesis method of lithium vanadium phosphate/carbon nanometer composite mesoporous microspheres as positive electrode material of lithium ion battery - Google Patents
Biomimetic synthesis method of lithium vanadium phosphate/carbon nanometer composite mesoporous microspheres as positive electrode material of lithium ion battery Download PDFInfo
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Abstract
The invention relates to a preparation method of lithium vanadium phosphate/carbon nanometer composite mesoporous microspheres as positive electrode material of a lithium ion battery. The preparation method comprises the following steps: preparing hungry green algae cell solution from inexpensive green algae cells; adding vanadium oxalate solution into the hungry green algae cell solution dropwise; adding phosphate source and lithium source to obtain gel; drying to obtain lithium vanadium phosphate precursor; grinding lithium vanadium phosphate precursor; heating at about 450 DEG C in the nitrogen atmosphere; and heating to about 750 DEG C and preserving the temperature to obtain black powdered Li3V2(PO4)3/C nanometer composite mesoporous microspheres. The lithium vanadium phosphate/carbon nanometer composite mesoporous microspheres prepared by the invention can be used as the positive electrode material of the lithium ion battery, and can be used for preparing portable or power lithium ion battery.
Description
(1) technical field
The present invention relates to a kind of phosphoric acid vanadium lithium/carbon (Li with good electrical chemical property
3V
2(PO
4)
3/ C) the biomimetic synthesis method of nano combined mesoporous microsphere belongs to the anode material for lithium-ion batteries technical field.
(2) background technology
Phosphoric acid vanadium lithium (Li
3V
2(PO
4)
3) because of having cheap abundant, the Stability Analysis of Structures of raw material, discharge platform (average out to 4.0V) and theoretical energy density (780Wh/Kg) are higher, good reversibility; Memory-less effect, self discharge is little, has extended cycle life; Pollute for a short time, form and be important anode material for lithium-ion batteries.Phosphoric acid vanadium lithium has three can freely embed the lithium deviate from, makes its highest theoretical capacity reach 197mAh/g, and the high-voltage charge excellent in efficiency.Therefore, phosphoric acid vanadium lithium has caused that domestic and international people pay close attention to greatly, are considered to have the lithium ion battery of application potential.But lower ion and electronic conductivity owing to this body structure of material causes cause high-rate discharge ability relatively poor, have limited it and have been used as the practical application of power lithium-ion battery positive electrode.
At present, prior art for preparing Li
3V
2(PO
4)
3Several different methods is arranged, and Burba etc. adopt the synthetic Li of ion-exchange
3V
2(PO
4)
3, referring to: Burba C M, Frecg R.Vibrational spectroscopic studies of monoclinic and rhombohedral Li
3V
2(PO
4)
3[J] .Solid State Ionics, 2007,177:3445-3454..This method component is even, synthesis temperature is low, particle is thin, but exists building-up process complicated, and operation, shortcomings such as product batch quality stability is poor, cost height are grown, are not easy to the cycle; Employing carbothermic methods such as Saidi have been synthesized phosphoric acid vanadium lithium; Referring to:
M.Y., Barker J., Huang H.; Swoyer J.L.and Adamson G..; Performance characteristics of lithium vanadium phosphate as a cathode material for lithium-ion batteries, Journal of Power Sources, 2003; 119-121,266-272.Shortcomings such as this method can improve material conductivity, but exists the reaction time long, and product uniformity and bulk density are relatively poor; People such as Zhu utilize sol-gel process to synthesize phosphoric acid vanadium lithium, referring to: Zhu X.J., Liu Y.X.; Geng L.M.and Chen L.B.; Synthesis and performance of lithium vanadium phosphate as cathode materials for lithium ion batteries by a sol-gel method, Journal of Power Sources, 2008; 184 (2), 578-582.This method chemical uniformity is good, heat treatment temperature is low, particle diameter is little and narrowly distributing, be easy to control, but dry shrink big, suitability for industrialized production is difficult, synthesis cycle is long.
In addition, relevant at present synthetic Li
3V
2(PO
4)
3Material also has some patent documents open; For example; CN1785798A discloses a kind of method with the Prepared by Sol Gel Method phosphoric acid vanadium lithium, and this method utilizes organic ligand can form the principle of complex with metal-complexing, and initial feed is mixed under the molecule rank; The material granule that makes is less, and discharge capacity is higher; CN101106194A discloses the method for the outer carbon coated positive electrode of the synthetic phosphoric acid vanadium lithium matrix of a kind of nano particle post forming liquid phase method; The positive electrode purity that this method is operated easily, reduced cost and obtains is high, high, the good cycling stability of discharge capacity; Shortcoming is that operating procedure is various, and the production cycle is longer.
Above scientific and technical literature and patent document concentrate on the improvement of existing synthetic method and the modification aspect of phosphoric acid vanadium lithium; Main through raising conductivity such as doping, carbon coated; But these methods all exist intrinsic shortcoming; Like shortcoming such as synthesis temperature height, complex process, the cycle is long, condition is harsh, cost is high and synthetic phosphoric acid vanadium lithium chemical property be undesirable, the synthetic technology of phosphoric acid vanadium lithium material, aspect of performance are not seen has substantive breakthroughs.Synthetic phosphoric acid vanadium lithium is difficult to satisfy the needs of electrokinetic cell because of combination property is undesirable.At present,, be badly in need of having new synthetic technology, reduce synthetic cost, thereby satisfy the needs of new energy field anode material for lithium-ion batteries in the hope of further improving the combination property of phosphoric acid vanadium lithium both at home and abroad based on the market demand of lithium ion battery.
(3) summary of the invention
In order to solve phosphoric acid vanadium lithium conductivity and the low problem of conductivity that prior art exists, the present invention provides a kind of phosphoric acid vanadium lithium/carbon (Li with good electric chemistry combination property
3V
2(PO
4)
3/ C) the biomimetic synthesis method of nano combined mesoporous microsphere material.Gained phosphoric acid vanadium lithium/carbon (Li
3V
2(PO
4)
3/ C) nano combined mesoporous microsphere material is as anode material for lithium-ion batteries
The present invention is with biotechnology and chemical synthesis process realization combining the object of the invention.
Technical scheme of the present invention is following:
A kind of Li
3V
2(PO
4)
3The nano combined mesoporous microsphere preparation methods of/C, step is following:
(1) preparation chlorella cell solution
2～10ml places 50～100ml distilled water with green alga algae liquid, and every 3h changes water once, under 25 ℃ of conditions, handles 1 day, makes chlorella cell be in starvation, and makes that cell concentration is 6 * 10 in the solution
7Individual/ml～9 * 10
7Individual/ml, obtain hungry chlorella cell solution, be designated as A solution.Said green alga is Chlorococcum (chroococcus) or chlorella (Chlorella) frond.
(2) preparation vanadium ion solution
The oxide and the reducing agent of pentavalent vanadium are dissolved in the distilled water by 1: 2～3 mol ratios, and under 70～90 ℃, fully stir 0.5～1 hour, obtain the vanadium ion solution of 0.05～2.5mol/L, be designated as B solution.
(3) under stirring condition, press B solution: A solution=1: 1～4 volume ratios, B solution is dropwise joined in the A solution, and stirred 1～5 hour, obtain the C sol solution.
(4) according to Li
3V
2(PO
4)
3Stoichiometric proportion, in the C sol solution, adding concentration is the source of phosphoric acid of 0.5mol/L, and fully stirs 1～5h, and then to add concentration be the lithium source of 0.8mol/L, and under 60～90 ℃ of water bath condition, fully stirs 1～5h, obtains the D gel.
(5) with the D gel in 70～150 ℃ dry 12～72 hours down, obtain the phosphoric acid vanadium lithium presoma.
(6),, obtain Li being warming up to 500～900 ℃ of heat treatments 6～12 hours after 3～5 hours again through 400～500 ℃ of heat treatments under the nitrogen atmosphere condition with above-mentioned phosphoric acid vanadium lithium presoma
3V
2(PO
4)
3The nano combined mesoporous microsphere powder of/C.
According to the present invention, the green alga algae liquid in the step (1) is that Chlorococcum (chroococcus) or chlorella (Chlorella) algae kind are carried out the cell cultivation by prior art, and the algae liquid that is in exponential phase of growth that obtains is also referred to as fresh green alga algae liquid.
According to the present invention, preferred, cell concentration is 6.5 * 10 in the middle gained solution of step (1)
7Individual/ml.
According to the present invention, preferred, the oxide of pentavalent vanadium is a vanadic oxide described in the step (2); Said reducing agent is an oxalic acid.
According to the present invention, preferred, the mol ratio of the oxide of pentavalent vanadium and reducing agent is 1: 2 described in the step (2).
According to the present invention, preferred, the said source of phosphoric acid (PO in the step (4)
4 3-) be selected from ammonium dihydrogen phosphate, diammonium hydrogen phosphate or phosphoric acid, wherein special preferably phosphoric acid ammonium dihydrogen; Said lithium source is lithium nitrate, lithium hydroxide, lithium acetate or lithium formate etc., wherein preferred especially lithium nitrate.
According to the present invention, preferred, the phosphoric acid vanadium lithium presoma obtains the good Li of chemical property behind 400 ℃ of heat treatment 5h, being warming up to 750 ℃ of insulation 6.5h under the nitrogen atmosphere condition again in the step (6)
3V
2(PO
4)
3The nano combined mesoporous microsphere powder of/C.
Further preferred, a kind of Li
3V
2(PO
4)
3The nano combined mesoporous microsphere preparation methods of/C, step is following:
The fresh green alga algae liquid 2ml that Chlorococcum (chroococcus) the algae kind of 1) getting the chlorella (Chlorella) that is numbered FACHB-1227 or being numbered FACHB-193 prepares; Place 50ml distilled water; Every 3h changes water once; Hungry continuously the processing one day under 25 ℃ of conditions, and get hungry chlorella cell solution, cell concentration is 6.5x10 in the control solution
7Individual/ml, be designated as A solution;
2) will analyze in pure vanadic oxide and the water-soluble solution of oxalic acid according to 1: 2 mol ratio, the about 0.5h of heated and stirred under 70 ℃ of water-baths, the vanadium ion solution of preparation 1mol/L obtains B solution;
3) press B solution: A solution=1: 2 volume ratio, solution B is dropwise joined in the solution A, fully stir 5h, obtain the C sol solution;
4) according to Li
3V
2(PO
4)
3Stoichiometric proportion adds the 0.5mol/L ammonium dihydrogen phosphate in the C sol solution, fully stir 5h after, add 0.8mol/L lithium nitrate or lithium hydroxide again, after fully stirring 5h under 70 ℃ of water bath condition, form the D gel; Dry 12h under 80 ℃ obtains the phosphoric acid vanadium lithium presoma; With the phosphoric acid vanadium lithium presoma grind the back in the nitrogen atmosphere protection down in 400 ℃ of heat treatment 5h, be warmed up to 750 ℃ again and be incubated 6.5h, obtain black powder Li
3V
2(PO
4)
3The nano combined mesoporous microsphere powder of/C.
The preparation of described green alga algae liquid is by prior art; For example: get chlorella (Chlorella) or Chlorococcum (chroococcus) algae kind chlorella cell; In GXZ intelligent illumination incubator, cultivate, adopt the BG11 medium culture, BG11 culture medium prescription: NaNO
31.500gL
-1, K
2HPO
40.040gL
-1, MgSO
47H
2O 0.075gL
-1, CaCl
22H
2O0.036gL
-1, citric acid 0.006gL
-1, ferric citrate 0.006gL
-1, EDTANa
20.001gL
-1, Na
2CO
30.020gL
-1, A5 solution * 1mL; * A5 solution formula (g/L): H
3BO
32.86, MnCl
24H
2O 1.86, ZnSO
47H
2O0.22, Na
2MoO
42H
2O 0.39, CuSO
45H
2O 0.08, Co (NO
3)
26H
2O 0.05.Intensity of illumination 2000lx, 25 ℃ of cultivation temperature, Light To Dark Ratio 12: 12, salinity 21.6, pH8.16, every day, regularly manual work was shaken 6 times, and the algae liquid of getting exponential phase of growth is as green alga algae liquid, and is subsequent use.
Technical characterstic of the present invention is that biotechnology is combined with sol-gal process; Vanadium source, source of phosphoric acid, lithium source are mixed with hungry chlorella cell solution; Because cell is the chlorella cell that is in starvation of under the environment of no nutrient, handling 1 day gained continuously, Fig. 2 b (sees) so that ion adsorbs to deposit on the green alga sphaerocyst more easily in institute.Form the Li of 20～50nm after the heat treatment
3V
2(PO
4)
3Particle and 15～-carbon granule (seeing Fig. 3 d) of 30nm, Li
3V
2(PO
4)
3The compound stable mesoporous microsphere structure (seeing Fig. 3 c) of being piled into of particle and carbon granule in-situ nano, thus realize the bionical synthetic of phosphoric acid vanadium lithium.Chlorella cell has not only played the effect of formation mesoporous microsphere stay in place form and (has seen Fig. 2 a), and be preparation Li in bionical building-up process
3V
2(PO
4)
3The nano combined mesoporous microsphere of/C provides conduction carbon source and nano particle binding agent, thereby has improved bulk density, conductivity and the specific capacity of phosphoric acid vanadium lithium/carbon nano-composite material.
The Li that the inventive method is prepared
3V
2(PO
4)
3The nano combined mesoporous microsphere particle diameter of/C is 2～6 microns, is to be piled up by the spheric granules of 15～50nm to form, and its mesoporous aperture is about 2～26nm, and porosity is 10～13%, and phosphorus content is 7～12%, and bulk density can reach 1.20～1.60g/cm
3, conductivity is 6.500～7.500 * 10
-3S/cm; Charging/discharging voltage is respectively 3.0～-when 4.3V, 3.0～4.8V, 0.1C multiplying power first discharge specific capacity can reach 124～127mAh/g and 179～185mAh/g respectively, and its discharge conservation rate is respectively 94～96% and 88～93%.The specific capacity that circulates after 40 weeks is respectively 111～117mAh/g and 137～141mAh/g, and its conservation rate is respectively 86～89% and 73～78%.
The present invention and prior art are relatively; It is advantageous that and utilize cheap chlorella cell to be mesoporous microsphere stay in place form and conduction carbon source and nano particle binding agent; Adopt simple chlorella cell-collosol and gel synthesis technique, the bionical excellent nano combined mesoporous microsphere anode material for lithium-ion batteries of phosphoric acid vanadium lithium/carbon of chemical property that synthesized.The Li of the present invention's preparation
3V
2(PO
4)
3The nano combined mesoporous microsphere powder of/C can be used for preparing portable or power lithium-ion battery as positive electrode.
(4) description of drawings
Fig. 1 is the XRD spectra of embodiment 1～3 synthetic powder; Wherein a is the XRD analysis of embodiment 1 synthetic powder; B is the XRD analysis of embodiment 2 synthetic powders; C is the XRD analysis of embodiment 3 synthetic powders
Fig. 2 is that the structural representation (a) and the ionic adsorption of embodiment 1 medium green ball frustule deposits to the microscope picture (b) on the Chlorococcum cell
Fig. 3 is the transmission electron microscope picture (a) and (b) of the different amplification of embodiment 1 synthetic sample
Fig. 4 is the nitrogen adsorption desorption isothermal curve (a) and the pore size distribution curve (b) of embodiment 1 synthetic sample
(5) embodiment
Below in conjunction with embodiment the present invention is further specified, but be not limited thereto.
Press the fresh green alga algae of prior art for preparing liquid:
Used Chlorophyta algae kind is provided by aquatile research institute of Chinese Academy of Sciences algae kind storehouse (FACHB-Collection) among the embodiment.The chlorella vulgaris that provides (Chlorella) deposit number is FACHB-1227, source: East Lake, Wuchang; Chlorococcum (chroococcus) deposit number is FACHB-193, source: East Lake, Wuchang.Chlorella cell is cultivated and in GXZ intelligent illumination incubator, is carried out, and adopts the BG11 medium culture, BG11 culture medium prescription: NaNO
31.500gL
-1, K
2HPO
40.040gL
-1, MgSO
47H
2O 0.075gL
-1, CaCl
22H
2O 0.036gL
-1, citric acid 0.006gL
-1, ferric citrate 0.006gL
-1, EDTANa
20.001gL
-1, Na
2CO
30.020gL
-1, A5 solution * 1mL; * A5 solution formula (g/L): H
3BO
32.86, MnCl
24H
2O 1.86, ZnSO
47H
2O 0.22, Na
2MoO
42H
2O 0.39, CuSO
45H
2O 0.08, Co (NO
3)
26H
2O 0.05.Intensity of illumination 2000lx, 25 ℃ of cultivation temperature, Light To Dark Ratio 12: 12, salinity 21.6, pH8.16, every day, regularly manual work was shaken 6 times, got the algae liquid of exponential phase of growth, was called fresh green alga algae liquid in an embodiment, and is subsequent use.
Embodiment 1,
Get the fresh green alga algae liquid 2ml that chlorella (Chlorella) the algae kind that is numbered FACHB-1227 prepares; Place 50ml distilled water, every 3h changes water once, hungry continuously the processing one day under 25 ℃ of conditions; And getting hungry chlorella cell solution, cell concentration is 6.5 * 10 in the control solution
7Individual/ml, be designated as A solution.
To analyze in pure vanadic oxide and the water-soluble solution of oxalic acid according to 1: 2 mol ratio, the about 0.5h of heated and stirred under 70 ℃ of water-baths, the vanadium ion solution of preparation 1mol/L obtains B solution.
Press B solution: A solution=1: 2 volume ratio, solution B is dropwise joined in the solution A, fully stir 5h, obtain the C sol solution.
According to Li
3V
2(PO
4)
3Stoichiometric proportion adds the 0.5mol/L ammonium dihydrogen phosphate in the C sol solution, fully stir 5h after, add 0.8mol/L lithium nitrate (lithium source) again, after fully stirring 5h under 70 ℃ of water bath condition, form the D gel; Dry 12h under 80 ℃ obtains the phosphoric acid vanadium lithium presoma.With the phosphoric acid vanadium lithium presoma grind the back in the nitrogen atmosphere protection down in 400 ℃ of heat treatment 5h, be warmed up to 750 ℃ again and be incubated 6.5h, obtain black powder Li
3V
2(PO
4)
3The nano combined mesoporous microsphere of/C.Through X-ray diffraction analysis is monoclinic form Li
3V
2(PO
4)
3With the complex of C, shown in Fig. 1 a; Fig. 3 a TEM photo shows, Li
3V
2(PO
4)
3/ C composite granule particle is meso-hole structure, and grain diameter is 2～6 microns, and grain structure is the spherical Li by 20-50nm
3V
2(PO
4)
3The spherical carbon granule of particle and 15-30nm is piled up and is formed, shown in Fig. 3 b; Can be known that by adsorption-desorption isothermal curve and pore size distribution curve analysis contain in the synthetic sample and have two kinds of meso-hole structures, its aperture, bottleneck hole is about 2～10nm, the open pore aperture is about 18～26nm, shown in Fig. 4 ab; Synthetic its porosity of composite granule is 11%, and phosphorus content is 7.9%, and bulk density can reach 1.56g/cm
3, conductivity is 6.793 * 10
-3S/cm; When charging/discharging voltage was respectively 3.0～4.3V, 3.0～4.8V, 0.1C multiplying power first discharge specific capacity can reach 127mAh/g and 185mAh/g respectively, and its discharge conservation rate is respectively 96% and 93%.The specific capacity that circulates after 40 weeks is respectively 117mAh/g and 141mAh/g, and its conservation rate is respectively 89% and 78%.
Embodiment 2,
Of embodiment 1, different is that lithium hydroxide is replaced by in lithium nitrate lithium source, and other conditions are with embodiment 1.Gained black powder Li
3V
2(PO
4)
3The nano combined mesoporous microsphere of/C, product show to be monoclinic form Li through XRD analysis
3V
2(PO
4)
3With the complex of C, shown in Fig. 1 b.Synthetic its bulk density of composite granule can reach 1.51g/cm
3, conductivity is 6.507 * 10
-3When S/cm, charging/discharging voltage were respectively 3.0～4.3V, 3.0～4.8V, 0.1C multiplying power first discharge specific capacity can reach 124mAh/g and 183mAh/g respectively, and its discharge conservation rate is respectively 95% and 91%.The specific capacity that circulates after 40 weeks is respectively 115mAh/g and 140mAh/g, and its conservation rate is respectively 88% and 76%.
Embodiment 3,
Of embodiment 1, different is that lithium acetate is replaced by in lithium nitrate lithium source, and other conditions are with embodiment 1.Gained black powder Li
3V
2(PO
4)
3The nano combined mesoporous microsphere of/C, product show to be monoclinic form Li through XRD analysis
3V
2(PO
4)
3With the complex of C, shown in Fig. 1 c.Synthetic its bulk density of composite granule can reach 1.35g/cm
3, conductivity is 1.915 * 10
-4When S/cm, charging/discharging voltage were respectively 3.0～4.3V, 3.0～4.8V, 0.1C multiplying power first discharge specific capacity can reach 104mAh/g and 173mAh/g respectively, and its discharge conservation rate is respectively 92% and 89%.The specific capacity that circulates after 40 weeks is respectively 97mAh/g and 139mAh/g, and its conservation rate is respectively 86% and 75%.
Embodiment 4,
Of embodiment 1, different is by B solution: A solution=1: 4 volume ratio, solution B is dropwise joined in the solution A, and fully stir 5h, obtain the C sol solution.Other operating conditions are with embodiment 1.Products therefrom shows to be monoclinic form Li through XRD analysis
3V
2(PO
4)
3Complex with C.Synthetic its bulk density of composite granule can reach 1.31g/cm
3, conductivity is 7.403 * 10
-3When S/cm, charging/discharging voltage were respectively 3.0～4.3V, 3.0～4.8V, 0.1C multiplying power first discharge specific capacity can reach 126mAh/g and 179mAh/g respectively, and its discharge conservation rate is respectively 94% and 88%.The specific capacity that circulates after 40 weeks is respectively 111mAh/g and 137mAh/g, and its conservation rate is respectively 86% and 73%.
Embodiment 5,
Of embodiment 1, different is with the algae fluid exchange is the fresh green alga algae liquid that Chlorococcum (chroococcus) the algae kind that is numbered FACHB-193 prepares.Other conditions are with embodiment 1.Li
3V
2(PO
4)
3The nano combined mesoporous microsphere of/C, product show to be monoclinic form Li through XRD analysis
3V
2(PO
4)
3Complex with C.Synthetic its bulk density of composite granule can reach 1.55g/cm
3, conductivity is 5.503 * 10
-3When S/cm, charging/discharging voltage were respectively 3.0～4.3V, 3.0～4.8V, 0.1C multiplying power first discharge specific capacity can reach 126mAh/g and 182mAh/g respectively, and its discharge conservation rate is respectively 96% and 90%.The specific capacity that circulates after 40 weeks is respectively 113mAh/g and 138mAh/g, and its conservation rate is respectively 89% and 75%.
Embodiment 6,
Get the fresh green alga algae liquid 5ml that Chlorococcum (chroococcus) the algae kind that is numbered FACHB-193 prepares; Place 70ml distilled water, every 3h changes water once, hungry continuously the processing one day under 25 ℃ of conditions; Get hungry chlorella cell solution, cell concentration is 7 * 10 in the control solution
7Individual/ml, be designated as A solution.Other conditions are with embodiment 1.Li
3V
2(PO
4)
3The nano combined mesoporous microsphere of/C, product show to be monoclinic form Li through XRD analysis
3V
2(PO
4)
3Complex with C.Synthetic its bulk density of composite granule can reach 1.40g/cm
3, conductivity is 4.517 * 10
-3When S/cm, charging/discharging voltage were respectively 3.0～4.3V, 3.0～4.8V, 0.1C multiplying power first discharge specific capacity can reach 125mAh/g and 182mAh/g respectively, and its discharge conservation rate is respectively 91% and 89%.The specific capacity that circulates after 40 weeks is respectively 105mAh/g and 137mAh/g, and its conservation rate is respectively 87% and 77%.
Claims (8)
1. Li
3V
2(PO
4)
3The nano combined mesoporous microsphere preparation methods of/C, step is following:
(1) preparation chlorella cell solution
2～10ml green alga algae liquid is placed 50～100ml distilled water, and every 3h changes water once, continuously hungry the processing 1 day under 25 ℃ of conditions, and make that cell concentration is 6 * 10 in the solution
7Individual/ml～9 * 10
7Individual/ml, obtain hungry chlorella cell solution, be designated as A solution; Said green alga is Chlorococcum (chroococcus) or chlorella (Chlorella) frond;
(2) preparation vanadium ion solution
The oxide and the reducing agent of pentavalent vanadium are dissolved in the distilled water by 1: 2～3 mol ratios, and under 70～90 ℃, fully stir 0.5～1 hour, obtain the vanadium ion solution of 0.05～2.5mol/L, be designated as B solution;
(3) under stirring condition, press B solution: A solution=1: 1～4 volume ratios, B solution is dropwise joined in the A solution, and stirred 1～5 hour, obtain the C sol solution;
(4) according to Li
3V
2(PO
4)
3Stoichiometric proportion, in the C sol solution, adding concentration is the source of phosphoric acid of 0.5mol/L, and fully stirs 1～5h, and then to add concentration be the lithium source of 0.8mol/L, and under 60～90 ℃ of water bath condition, fully stirs 1～5h, obtains the D gel;
(5) with the D gel in 70～150 ℃ dry 12～72 hours down, obtain the phosphoric acid vanadium lithium presoma;
(6),, obtain Li being warming up to 500～900 ℃ of heat treatments 6～12 hours after 3～5 hours again through 400～500 ℃ of heat treatments under the nitrogen atmosphere condition with above-mentioned phosphoric acid vanadium lithium presoma
3V
2(PO
4)
3The nano combined mesoporous microsphere powder of/C.
2. preparation method according to claim 1 is characterized in that the green alga algae liquid in the step (1) is that Chlorococcum (chroococcus) or chlorella (Chlorella) algae kind are carried out the algae liquid that is in exponential phase of growth that the cell cultivation obtains by prior art.
3. preparation method according to claim 1 is characterized in that cell concentration is 6.5 * 10 in the middle gained solution of step (1)
7Individual/ml.
4. preparation method according to claim 1 is characterized in that the oxide of pentavalent vanadium described in the step (2) is a vanadic oxide; Said reducing agent is an oxalic acid.
5. preparation method according to claim 1 is characterized in that the oxide of pentavalent vanadium described in the step (2) and the mol ratio of reducing agent are 1: 2.
6. preparation method according to claim 1 is characterized in that the said source of phosphoric acid in the step (4) is ammonium dihydrogen phosphate, diammonium hydrogen phosphate or phosphoric acid, wherein the preferably phosphoric acid ammonium dihydrogen; Said lithium source is lithium nitrate, lithium hydroxide, lithium acetate or lithium formate, wherein preferred lithium nitrate.
7. preparation method according to claim 1 is characterized in that the phosphoric acid vanadium lithium presoma obtains the good Li of chemical property behind 400 ℃ of heat treatment 5h, being warming up to 750 ℃ of insulation 6.5h under the nitrogen atmosphere condition again in the step (6)
3V
2(PO
4)
3The nano combined mesoporous microsphere powder of/C.
8. preparation method according to claim 1 is characterized in that step is following:
The fresh green alga algae liquid 2ml that Chlorococcum (chroococcus) the algae kind of getting the chlorella (Chlorella) that is numbered FACHB-1227 or being numbered FACHB-193 prepares; Place 50ml distilled water; Every 3h changes water once; Hungry continuously the processing one day gets hungry chlorella cell solution under 25 ℃ of conditions, and cell concentration is 6.5 * 10 in the control solution
7Individual/ml, be designated as A solution;
To analyze in pure vanadic oxide and the water-soluble solution of oxalic acid according to 1: 2 mol ratio, the about 0.5h of heated and stirred under 70 ℃ of water-baths, the vanadium ion solution of preparation 1mol/L obtains B solution;
Press B solution: A solution=1: 2 volume ratio, solution B is dropwise joined in the solution A, fully stir 5h, obtain the C sol solution;
According to Li
3V
2(PO
4)
3Stoichiometric proportion adds the 0.5mol/L ammonium dihydrogen phosphate in the C sol solution, fully stir 5h after, add 0.8mol/L lithium nitrate or lithium hydroxide again, after fully stirring 5h under 70 ℃ of water bath condition, form the D gel; Dry 12h under 80 ℃ obtains the phosphoric acid vanadium lithium presoma; With the phosphoric acid vanadium lithium presoma grind the back in the nitrogen atmosphere protection down in 400 ℃ of heat treatment 5h, be warmed up to 750 ℃ again and be incubated 6.5h, obtain black powder Li
3V
2(PO
4)
3The nano combined mesoporous microsphere powder of/C.
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