CN104282891A - Method for synthesizing lithium vanadium phosphate/carbon composite material by adopting one-step sol-gel method - Google Patents
Method for synthesizing lithium vanadium phosphate/carbon composite material by adopting one-step sol-gel method Download PDFInfo
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Abstract
The invention discloses a method for synthesizing a lithium vanadium phosphate/carbon composite material by adopting a one-step sol-gel method. The method comprises the following steps: directly mixing a lithium source chemical compound, a vanadium resource chemical compound, a phosphorus resource chemical compound, a chelating agent and a carbon source to obtain a mixture; adding the mixture into a sealing container; adding deionized water into the sealing container; heating while stirring so as to obtain a dry sol precursor mixture; and sintering the dry sol precursor mixture under an inert gas protective atmosphere and a reducing mixed gas protective atmosphere in sequence, so as to obtain the lithium vanadium phosphate/carbon composite material with high performances. The method is simple, is easy to operate, has the advantages that the synthesizing temperature is low, the product uniformity is good, the product grain size is small, and the product electrochemical performance is good when the sol-gel method is adopted, and can overcome the defects that the sol-gel method is complex and tedious in operation, large in pollution and low in cost; the solution reaction is carried out in the sealing container, so that the bumping and splashing caused by over violence in the reaction process can be effectively restrained and prevented, and the controllability and the accuracy of tests can be further improved.
Description
Technical field
The present invention relates to nano material synthesis and electrochemical techniques applied technical field, be specifically related to the method for a step sol-gal process synthesized high-performance vanadium phosphate lithium/carbon composite material.
Background technology
Lithium ion battery is not only applied to battery and the energy storage device of portable electric appts now, is also used to Developing Hybrid Vehicle Industry to substitute existing fossil fuel power vehicle.Therefore, compared to the lithium ion battery negative material closely becoming ripe, positive electrode directly governs the research and apply of lithium ion battery.
After lead accumulator, nickel-cadmium cell, cobalt acid lithium battery, lithium manganate battery and polyanionic battery, the LiFePO4 (LiFePO of the olivine structural of phosphorous acid group
4) discovery bring revolution to lithium ion battery industry.The LiFePO4 of olivine structural have security and stability good, have extended cycle life, cheap advantage, but its electronic and ionic poorly conductive, lithium ion diffusion coefficient is low and heavy-current discharge characteristic is poor critical defect allow its application be subject to great restriction.
There is the phosphoric acid vanadium lithium (Li with LiFePO4 similar structures
3v
2(PO
4)
3) material not only has the fail safe more similar than LiFePO4 and cyclical stability, and have higher electronic and ionic conductivity, theoretical charge/discharge capacity and charging/discharging voltage platform, therefore its positive electrode as lithium-ion-power cell has better application prospect.The modal method of current synthesis vanadium phosphate cathode material has solid-phase synthesis, hydrothermal synthesis method, microwave process for synthesizing, sol-gel process etc.Wherein solid-phase synthesis not only needs the reaction time of at substantial and very high temperature, and obtained product grain is large and uneven.Hydrothermal synthesis method has strict requirement to equipment and raw material, and generated time is long, is difficult to realize large-scale production in enormous quantities.Conventional sol-gel rule synthesis cycle is long, operates more complicated, severe reaction conditions.
Summary of the invention
The technical problem to be solved in the present invention is the deficiency overcoming prior art existence, a kind of method of a step sol-gal process synthesis vanadium phosphate lithium/carbon composite material is provided, the technique of the method is simple, be easy to operation, not only possess the advantage that sol-gal process synthesis temperature is low, the good particle diameter of product uniformity is little, chemical property is good, and overcome the shortcoming that sol-gal process complicated operation is loaded down with trivial details, pollution is large and cost is low; And under closed container, carry out solution reaction, can effectively suppress and prevent because course of reaction is too violent and produce bumping, splash, controllability and the accuracy of experiment can be increased further.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A method for one step sol-gal process synthesis vanadium phosphate lithium/carbon composite material, comprises the following steps:
(1) Li source compound, vanadium source compound, P source compound, chelating agent and carbon source stoichiometrically being taken rear mixing loads in closed container, in closed container, add ionized water, stir 0.5 ~ 2h at 60 ~ 90 DEG C of temperature lower magnetic forces and obtain solidliquid mixture;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 4 ~ 24h, obtain xerogel precursor mixture;
(3) will proceed in heating furnace after the xerogel precursor mixture obtained grinding evenly, in inert gas shielding atmosphere, be warmed up to 300 ~ 500 DEG C with the heating rate of 1 ~ 10 DEG C/min carry out calcining at constant temperature, after calcining at constant temperature 3 ~ 6h, cooling obtains precursor powder naturally; In this step, 15 ~ 30min is preferably to the milling time of xerogel precursor mixture; Inert gas preferably passes into heating furnace with the speed of 100 ~ 1000mL/min;
(4) will proceed in heating furnace after the precursor powder obtained grinding evenly; in reducibility gas protective atmosphere, be warmed up to 700 ~ 900 DEG C with 1 ~ 10 DEG C/min heating rate carry out calcining at constant temperature, after calcining at constant temperature 6 ~ 12h, obtain vanadium phosphate lithium/carbon composite material.In this step, 30 ~ 120min is preferably to the milling time of xerogel precursor mixture; Reducibility gas preferably passes into heating furnace with the speed of 100 ~ 1000mL/min;
In said method, preferably, described Li source compound is lithium dihydrogen phosphate, lithium carbonate, lithium nitrate, lithium hydroxide, lithium acetate or lithium sulfate.
In said method, preferably, described vanadium source compound is vanadic oxide or ammonium metavanadate.
In said method, preferably, described P source compound is lithium dihydrogen phosphate, ammonium di-hydrogen phosphate, DAP or ammonium phosphate.
In said method, preferably, described chelating agent to be oxalic acid, citric acid or mass ratio be 30% hydrogen peroxide.
In said method, preferably, described carbon source is any one or more any molar mixture in acetylene black, graphite powder, superconduction carbon black, citric acid and solvable carbohydrate, and wherein carbon content accounting is 3 ~ 15% of the quality of the vanadium phosphate lithium/carbon composite material generated.
In said method, preferably, described inert gas is argon gas or nitrogen; Described reducibility gas is the mist of argon gas, CO (carbon monoxide converter) gas, nitrogen and hydrogen, and wherein hydrogen or CO (carbon monoxide converter) gas account for 2 ~ 8% of mist volume.
In said method, preferably, the described closed container closed glass jar that is the blue bottle of silk, ground flask or adds a cover; Described heating furnace is tube furnace.
In said method, preferably, also have the step that the solidliquid mixture that obtains after to step (1) processes further before the step (2), process refers to and adopts ultrasonic disperse, hydro-thermal, adjustment solution pH value and at least one processing method of adding in surfactant to process solidliquid mixture further.
In said method, preferably, the processing time of described ultrasonic disperse process is 0.5 ~ 6h; The temperature of described hydrothermal treatment consists is 180 ~ 240 DEG C, and temperature retention time is 2 ~ 40h; The pH value adjustable range of described adjustment solution pH value process is 2 ~ 11; The surfactant that the process of described interpolation surfactant adopts is cetyl trimethyl quaternary ammonium bromides, cetyl trimethyl amine, hydrazine hydrate or polyethylene glycol.
Compared with prior art, the invention has the advantages that:
1, method of the present invention adopts one-step method sol-gal process synthesis of high purity and crystalline vanadium phosphate lithium/carbon composite material, its technique is simple, be easy to operation, be applicable to suitability for industrialized production, not only possess the advantage that sol-gal process synthesis temperature is low, the good particle diameter of product uniformity is little, chemical property is good, and overcome the shortcoming that conventional sol gel synthesis cycle is long, complicated operation is loaded down with trivial details, pollution is large and cost is high;
2, the present invention carries out solution reaction under closed container, can effectively suppress and prevent the phenomenon producing bumping and splash because course of reaction is too violent, can increase controllability and the accuracy of experiment further;
3, the charcoal in the present invention adds at solution state, not only effectively can increase the contact between charcoal and active material, and at heat treatment stages, effectively can suppress the oxidation of vanadium in product phosphoric acid vanadium lithium, thus ensure the generation of active material, also effectively suppressing growing up and improving the chemical property of product of crystal grain simultaneously, the selectivity of inert atmosphere even can being made larger, as not necessarily needed by reducing atmosphere;
4, the present invention can adopt multiple processing method to be further processed the solidliquid mixture obtained after step (1), not only greatly can improve the performance of product each side and the multiple processing method of parallel study to the impact of properties of product, and multiple processing method also can coordinate employing simultaneously, make technique simpler, operability is better, and the positive electrode that prepared vanadium phosphate lithium/carbon composite material is used as lithium ion battery has very excellent chemical property;
5, the present invention can also increase reaction speed by increasing reaction temperature, effectively can shorten reaction time like this, also make reaction more abundant simultaneously.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the vanadium phosphate lithium/carbon composite material that the embodiment of the present invention 1 obtains.
Fig. 2 is the electrical property curve chart of the vanadium phosphate lithium/carbon composite material that the embodiment of the present invention 1 obtains.
Fig. 3 is the XRD figure of the vanadium phosphate lithium/carbon composite material that the embodiment of the present invention 2 obtains.
Fig. 4 is the electrical property curve chart of the vanadium phosphate lithium/carbon composite material that the embodiment of the present invention 2 obtains.
Fig. 5 is the XRD figure of the vanadium phosphate lithium/carbon composite material that the embodiment of the present invention 3 obtains.
Fig. 6 is the XRD figure of the vanadium phosphate lithium/carbon composite material that the embodiment of the present invention 4 obtains.
Fig. 7 is the XRD figure of the vanadium phosphate lithium/carbon composite material that the embodiment of the present invention 5 obtains.
Fig. 8 is the XRD figure of the vanadium phosphate lithium/carbon composite material that the embodiment of the present invention 6 obtains.
Fig. 9 is the XRD figure of the vanadium phosphate lithium/carbon composite material that the embodiment of the present invention 7 obtains.
Figure 10 is the XRD figure of the vanadium phosphate lithium/carbon composite material that the embodiment of the present invention 8 obtains.
Figure 11 is the XRD figure of the vanadium phosphate lithium/carbon composite material that the embodiment of the present invention 9 obtains.
Embodiment
Below in conjunction with specific embodiment and Figure of description, the present invention is described in further detail.
Embodiment 1
The method of the one step sol-gal process synthesis vanadium phosphate lithium/carbon composite material of the present embodiment comprises the following steps:
(1) by V
2o
5, H
2c
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4take 2.00g, 4.16g, 1.22g, 3.79g respectively by the stoichiometric proportion of 1:3:1.5:3 and load closed container, section's qin superconduction carbon black that the amount being 10% according to the mass ratio of amorphous carbon in the active material (vanadium phosphate lithium/carbon composite material) generated again takes 0.56g loads closed container, and 500ml deionized water is added in closed container, stir 1h at 60 ~ 90 DEG C of temperature lower magnetic forces and obtain solidliquid mixture;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 8h, obtain xerogel precursor mixture;
(3) proceed in tube furnace after the xerogel precursor mixture grinding evenly step (2) obtained, the inert gas formation inert gas shielding atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace, and make tube furnace be warmed up to 350 DEG C with the heating rate of 5 DEG C/min to carry out calcining at constant temperature, after calcining at constant temperature 4h, cooling obtains precursor powder naturally; In this step, milling time is preferably 30min;
(4) proceed to again in tube furnace after the precursor powder grinding evenly step (3) obtained; the reproducibility mist formation reducibility gas protective atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace; and make tube furnace be warmed up to 800 DEG C with 5 DEG C/min heating rate to carry out calcining at constant temperature, after calcining at constant temperature 8h, obtain vanadium phosphate lithium/carbon composite material.In this step, milling time is preferably 60min.
The XRD result of the vanadium phosphate lithium/carbon composite material adopting the method for the present embodiment to obtain and chemical property are respectively as depicted in figs. 1 and 2.By diffraction maximum position in Fig. 1, intensity and width can be inferred, sintetics is the pure phase of phosphoric acid vanadium lithium, and the granularity of product is very little, crystallinity is also fine, also allows vanadium phosphate lithium/carbon composite material have very excellent chemical property (see Fig. 2) simultaneously.
Embodiment 2
The method of the one step sol-gal process synthesis vanadium phosphate lithium/carbon composite material of the present embodiment comprises the following steps:
(1) by V
2o
5, H
2c
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4take 2.00g, 4.16g, 1.22g, 3.79g respectively by the stoichiometric proportion of 1:3:1.5:3 and load closed container, section's qin superconduction carbon black that the amount being 10% according to the mass ratio of amorphous carbon in the active material generated again takes 0.56g loads closed container, and 500ml deionized water is added in closed container, stir 1h at 60 ~ 90 DEG C of temperature lower magnetic forces and obtain solidliquid mixture;
Carry out ultrasonic disperse process to the solidliquid mixture obtained, the processing time is 60min;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 8h, obtain xerogel precursor mixture;
(3) proceed in tube furnace after the xerogel precursor mixture grinding evenly step (2) obtained, the inert gas formation inert gas shielding atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace, and make tube furnace be warmed up to 350 DEG C with the heating rate of 5 DEG C/min to carry out calcining at constant temperature, after calcining at constant temperature 4h, cooling obtains precursor powder naturally; In this step, milling time is preferably 30min;
(4) proceed to again in tube furnace after the precursor powder grinding evenly step (3) obtained; the reproducibility mist formation reducibility gas protective atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace; and make tube furnace be warmed up to 800 DEG C with 5 DEG C/min heating rate to carry out calcining at constant temperature, after calcining at constant temperature 8h, obtain vanadium phosphate lithium/carbon composite material.In this step, milling time is preferably 60min.
The XRD result of the vanadium phosphate lithium/carbon composite material adopting the method for the present embodiment to obtain and chemical property are respectively as shown in Figure 3 and Figure 4.By diffraction maximum position in Fig. 3, intensity and width can be inferred, sintetics is the pure phase of phosphoric acid vanadium lithium, and the granularity of product is very little, crystallinity is also fine, also allows the vanadium phosphate lithium/carbon composite material of synthesis have very excellent chemical property (see Fig. 4) simultaneously.
Embodiment 3
The method of the one step sol-gal process synthesis vanadium phosphate lithium/carbon composite material of the present embodiment comprises the following steps:
(1) by V
2o
5, H
2c
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4take 0.200g, 0.416g, 0.122g, 0.379g respectively by the stoichiometric proportion of 1:3:1.5:3 and load closed container, section's qin superconduction carbon black that the amount being 10% according to the mass ratio of amorphous carbon in the active material generated again takes 0.056g loads closed container, and 50ml deionized water is added in closed container, stir at 60 ~ 90 DEG C of temperature lower magnetic forces and obtain solidliquid mixture;
Carry out ultrasonic disperse process to the solidliquid mixture obtained, the processing time is 60min, then to proceed in water heating kettle be incubated two hours at 180 DEG C;
(2) solidliquid mixture obtained is proceeded to open container to continue to add thermal agitation 8h, obtain xerogel precursor mixture;
(3) proceed in tube furnace after the xerogel precursor mixture grinding evenly step (2) obtained, the inert gas formation inert gas shielding atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace, and make tube furnace be warmed up to 350 DEG C with the heating rate of 5 DEG C/min to carry out calcining at constant temperature, after calcining at constant temperature 4h, cooling obtains precursor powder naturally; In this step, milling time is preferably 30min;
(4) proceed to again in tube furnace after the precursor powder grinding evenly step (3) obtained; the reproducibility mist formation reducibility gas protective atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace; and make tube furnace be warmed up to 800 DEG C with 5 DEG C/min heating rate to carry out calcining at constant temperature, after calcining at constant temperature 8h, obtain vanadium phosphate lithium/carbon composite material.In this step, milling time is preferably 60min.
As shown in Figure 5, comparative example 1 and embodiment 2, its diffraction peak intensity not only increases the XRD result of the vanadium phosphate lithium/carbon composite material adopting the method for the present embodiment to prepare, and its width also reduces, thus its crystallinity also increases greatly.
Embodiment 4
The method of the one step sol-gal process synthesis vanadium phosphate lithium/carbon composite material of the present embodiment comprises the following steps:
(1) by V
2o
5, H
2c
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4take 2.00g, 4.16g, 1.22g, 3.79g respectively by the stoichiometric proportion of 1:3:1.5:3 and load closed container, section's qin superconduction carbon black that the amount being 10% according to the mass ratio of amorphous carbon in the active material generated again takes 0.56g loads closed container, and 500ml deionized water is added in closed container, stir 1h at 60 ~ 90 DEG C of temperature lower magnetic forces and obtain solidliquid mixture;
By oxalic acid (H
2c
2o
4) pH value of the solidliquid mixture solution obtained is adjusted to 3 ~ 4, then carries out ultrasonic disperse process by solution, the processing time is 60min;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 8h, obtain xerogel precursor mixture;
(3) proceed in tube furnace after the xerogel precursor mixture grinding evenly step (2) obtained, the inert gas formation inert gas shielding atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace, and make tube furnace be warmed up to 350 DEG C with the heating rate of 5 DEG C/min to carry out calcining at constant temperature, after calcining at constant temperature 4h, cooling obtains precursor powder naturally; In this step, milling time is preferably 30min;
(4) proceed to again in tube furnace after the precursor powder grinding evenly step (3) obtained; the reproducibility mist formation reducibility gas protective atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace; and make tube furnace be warmed up to 800 DEG C with 5 DEG C/min heating rate to carry out calcining at constant temperature, after calcining at constant temperature 8h, obtain vanadium phosphate lithium/carbon composite material.In this step, milling time is preferably 60min.
As shown in Figure 6, comparative example 1 and embodiment 2, its diffraction peak intensity not only increases the XRD result of the vanadium phosphate lithium/carbon composite material adopting the method for the present embodiment to obtain, and its width also reduces, thus show that its crystallinity also increases greatly.The oxalic acid added in step (1) not only effectively can reduce heat treatment temperature, and the gas of excessive oxalic acid release can allow intergranular clearance rate increase.
Embodiment 5
The method of the one step sol-gal process synthesis vanadium phosphate lithium/carbon composite material of the present embodiment comprises the following steps:
(1) by V
2o
5, H
2c
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4take 2.00g, 4.16g, 1.22g, 3.79g respectively by the stoichiometric proportion of 1:3:1.5:3 and load closed container, section's qin superconduction carbon black that the amount being 10% according to the mass ratio of amorphous carbon in the active material generated again takes 0.56g loads closed container, and 500ml deionized water is added in closed container, stir 1h at 60 ~ 90 DEG C of temperature lower magnetic forces and obtain solidliquid mixture;
The pH value of the solidliquid mixture solution obtained is adjusted to 10 ~ 11, then carries out ultrasonic disperse process, the processing time is 60min;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 8h, obtain xerogel precursor mixture;
(3) proceed in tube furnace after the xerogel precursor mixture grinding evenly step (2) obtained, the inert gas formation inert gas shielding atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace, and make tube furnace be warmed up to 350 DEG C with the heating rate of 5 DEG C/min to carry out calcining at constant temperature, after calcining at constant temperature 4h, cooling obtains precursor powder naturally; In this step, milling time is preferably 30min;
(4) proceed to again in tube furnace after the precursor powder grinding evenly step (3) obtained; the reproducibility mist formation reducibility gas protective atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace; and make tube furnace be warmed up to 800 DEG C with 5 DEG C/min heating rate to carry out calcining at constant temperature, after calcining at constant temperature 8h, obtain vanadium phosphate lithium/carbon composite material.In this step, milling time is preferably 60min.
The XRD result of the vanadium phosphate lithium/carbon composite material adopting the method for the present embodiment to obtain as shown in Figure 7, diffraction maximum position in composition graphs, intensity and width can draw, sintetics is the pure phase of phosphoric acid vanadium lithium, and the granularity of product is very little, crystallinity is also fine.Solution is adjusted to alkalescence by acidity in (1) by step, effectively can improve the contact between phosphoric acid vanadium lithium and charcoal.
Embodiment 6
The method of the one step sol-gal process synthesis vanadium phosphate lithium/carbon composite material of the present embodiment comprises the following steps:
(1) by V
2o
5, H
2c
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4take 2.00g, 4.16g, 1.22g, 3.79g respectively by the stoichiometric proportion of 1:3:1.5:3 and load closed container, then take the C of 2.03g according to the amount that the mass ratio of amorphous carbon in the active material generated is 10%
12h
22o
11(sucrose) loads closed container, and adds 500ml deionized water in closed container, stirs 1h obtain solidliquid mixture at 60 ~ 90 DEG C of temperature lower magnetic forces;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 8h, obtain xerogel precursor mixture;
(3) proceed in tube furnace after the xerogel precursor mixture grinding evenly step (2) obtained, the inert gas formation inert gas shielding atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace, and make tube furnace be warmed up to 350 DEG C with the heating rate of 5 DEG C/min to carry out calcining at constant temperature, after calcining at constant temperature 4h, cooling obtains precursor powder naturally; In this step, milling time is preferably 30min;
(4) proceed to again in tube furnace after the precursor powder grinding evenly step (3) obtained; the reproducibility mist formation reducibility gas protective atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace; and make tube furnace be warmed up to 800 DEG C with 5 DEG C/min heating rate to carry out calcining at constant temperature, after calcining at constant temperature 8h, obtain vanadium phosphate lithium/carbon composite material.In this step, milling time is preferably 60min.
The XRD result of the vanadium phosphate lithium/carbon composite material adopting the method for the present embodiment to obtain as shown in Figure 8, by diffraction maximum position in Fig. 8, intensity and width can be inferred, sintetics is the pure phase of phosphoric acid vanadium lithium, and the granularity of product is very little, crystallinity is also fine.The present embodiment adopts soluble sugar sucrose as carbon source, can be wrapped in phosphoric acid vanadium lithium surface densely, thus can effectively suppress growing up of phosphoric acid vanadium lithium particle in carbonisation, so the granularity of product is very little and crystallinity is also very good.
Embodiment 7
The method of the one step sol-gal process synthesis vanadium phosphate lithium/carbon composite material of the present embodiment comprises the following steps:
(1) by V
2o
5, H
2c
2o
42H
2o, LiH
2pO
4take 2.00g, 4.16g, 1.22g, 3.43g respectively by the stoichiometric proportion of 1:3:3 and load closed container, then take the C of 2.03g according to the amount that the mass ratio of amorphous carbon in the active material generated is 10%
12h
22o
11(sucrose) loads closed container, and adds 500ml deionized water in closed container, stirs 1h obtain solidliquid mixture at 60 ~ 90 DEG C of temperature lower magnetic forces; LiH in the present embodiment
2pO
4simultaneously as Li source compound and P source compound;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 8h, obtain xerogel precursor mixture;
(3) proceed in tube furnace after the xerogel precursor mixture grinding evenly step (2) obtained, the inert gas formation inert gas shielding atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace, and make tube furnace be warmed up to 350 DEG C with the heating rate of 5 DEG C/min to carry out calcining at constant temperature, after calcining at constant temperature 4h, cooling obtains precursor powder naturally; In this step, milling time is preferably 30min;
(4) proceed to again in tube furnace after the precursor powder grinding evenly step (3) obtained; the reproducibility mist formation reducibility gas protective atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace; and make tube furnace be warmed up to 800 DEG C with 5 DEG C/min heating rate to carry out calcining at constant temperature, after calcining at constant temperature 8h, obtain vanadium phosphate lithium/carbon composite material.In this step, milling time is preferably 60min.
The XRD figure of the vanadium phosphate lithium/carbon composite material adopting the method for the present embodiment to obtain as shown in Figure 9, by diffraction maximum position in Fig. 9, can infer, sintetics is the pure phase of phosphoric acid vanadium lithium, and the granularity of product is very little, and crystallinity is also fine by intensity and width.Compare embodiment 6, the present embodiment adopts LiH
2pO
4replace ammonium dihydrogen phosphate and lithium carbonate, the precipitation of solution in evaporation process can be prevented, increase the dispersiveness of each component, thus the phosphoric acid vanadium lithium crystal grain that synthesis ratio embodiment 6 granularity is less, its crystallinity can be increased to a certain extent simultaneously.
Embodiment 8
The method of the one step sol-gal process synthesis vanadium phosphate lithium/carbon composite material of the present embodiment comprises the following steps:
(1) by V
2o
5, LiH
2pO
4take 2.00g, 3.43g respectively by the stoichiometric proportion of 1:3 and load closed container, adding about 10mL content (quality) is the hydrogen peroxide of 30%, section's qin superconduction carbon black that the amount being 10% according to the mass ratio of amorphous carbon in the active material generated again takes 0.56g loads closed container, and 500ml deionized water is added in closed container, stir 1h at 60 ~ 90 DEG C of temperature lower magnetic forces and obtain solidliquid mixture; LiH in the present embodiment
2pO
4simultaneously as Li source compound and P source compound;
Carry out ultrasonic disperse process to the solidliquid mixture obtained, the processing time is 60min;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 8h, obtain xerogel precursor mixture;
(3) proceed in tube furnace after the xerogel precursor mixture grinding evenly step (2) obtained, the inert gas formation inert gas shielding atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace, and make tube furnace be warmed up to 350 DEG C with the heating rate of 5 DEG C/min to carry out calcining at constant temperature, after calcining at constant temperature 4h, cooling obtains precursor powder naturally; In this step, milling time is preferably 30min;
(4) proceed to again in tube furnace after the precursor powder grinding evenly step (3) obtained; the reproducibility mist formation reducibility gas protective atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace; and make tube furnace be warmed up to 800 DEG C with 5 DEG C/min heating rate to carry out calcining at constant temperature, after calcining at constant temperature 8h, obtain vanadium phosphate lithium/carbon composite material.In this step, milling time is preferably 60min.
The XRD figure of the vanadium phosphate lithium/carbon composite material adopting the method for the present embodiment to obtain as shown in Figure 10, by diffraction maximum position in Figure 10, intensity and width can be inferred, sintetics is the pure phase of phosphoric acid vanadium lithium, and the granularity of product is very little, crystallinity is also fine.Compared to other embodiments, the present embodiment is in heating evaporation process, hydrogen peroxide can be formed as chelating agent and be uniformly dispersed and stable sol-gel, increases the dispersiveness of each composition and the controllability of course of reaction further, thus the phosphoric acid vanadium lithium product that synthesis performance is more excellent.
Embodiment 9
The method of the one step sol-gal process synthesis vanadium phosphate lithium/carbon composite material of the present embodiment comprises the following steps:
(1) by V
2o
5, CH
3cOOLi, NH
4h
2pO
4take 2.00g, 3.54g, 3.79g respectively by the stoichiometric proportion of 1:3:3 and load closed container, adding about 10mL content (quality) is the hydrogen peroxide of 30%, section's qin superconduction carbon black that the amount being 10% according to the mass ratio of amorphous carbon in the active material generated again takes 0.56g loads closed container, and 500ml deionized water is added in closed container, stir 1h at 60 ~ 90 DEG C of temperature lower magnetic forces and obtain solidliquid mixture;
Carry out ultrasonic disperse process to the solidliquid mixture obtained, the processing time is 60min;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 8h, obtain xerogel precursor mixture;
(3) proceed in tube furnace after the xerogel precursor mixture grinding evenly step (2) obtained, the inert gas formation inert gas shielding atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace, and make tube furnace be warmed up to 350 DEG C with the heating rate of 5 DEG C/min to carry out calcining at constant temperature, after calcining at constant temperature 4h, cooling obtains precursor powder naturally; In this step, milling time is preferably 30min;
(4) proceed to again in tube furnace after the precursor powder grinding evenly step (3) obtained; the reproducibility mist formation reducibility gas protective atmosphere that flow velocity is 300 ~ 500mL/min is passed in tube furnace; and make tube furnace be warmed up to 800 DEG C with 5 DEG C/min heating rate to carry out calcining at constant temperature, after calcining at constant temperature 8h, obtain vanadium phosphate lithium/carbon composite material.In this step, milling time is preferably 60min.
The XRD figure of the vanadium phosphate lithium/carbon composite material adopting the method for the present embodiment to obtain as shown in figure 11, by diffraction maximum position in Figure 11, intensity and width can be inferred, sintetics is the pure phase of phosphoric acid vanadium lithium, and the granularity of product is very little, crystallinity is also fine.Compared to other embodiments, the present embodiment is in heating evaporation process, hydrogen peroxide can be formed as chelating agent and be uniformly dispersed and stable sol-gel, increases the dispersiveness of each composition and the controllability of course of reaction further, thus the phosphoric acid vanadium lithium product that synthesis performance is more excellent.And lithium acetate can release portion gas and can be partially carbonized in heat treatment process, thus improve the chemical property of vanadium phosphate lithium/carbon composite material further.
Claims (10)
1. a method for a step sol-gal process synthesis vanadium phosphate lithium/carbon composite material, is characterized in that, comprise the following steps:
(1) Li source compound, vanadium source compound, P source compound, chelating agent and carbon source stoichiometrically being taken rear mixing loads in closed container, in closed container, add ionized water, stir 0.5 ~ 2h at 60 ~ 90 DEG C of temperature lower magnetic forces and obtain solidliquid mixture;
(2) closed container is opened and maybe the solidliquid mixture obtained is proceeded to open container and continue to add thermal agitation 4 ~ 24h, obtain xerogel precursor mixture;
(3) will proceed in heating furnace after the xerogel precursor mixture obtained grinding evenly, in inert gas shielding atmosphere, be warmed up to 300 ~ 500 DEG C with the heating rate of 1 ~ 10 DEG C/min carry out calcining at constant temperature, after calcining at constant temperature 3 ~ 6h, cooling obtains precursor powder naturally;
(4) will proceed in heating furnace after the precursor powder obtained grinding evenly; in reducibility gas protective atmosphere, be warmed up to 700 ~ 900 DEG C with 1 ~ 10 DEG C/min heating rate carry out calcining at constant temperature, after calcining at constant temperature 6 ~ 12h, obtain vanadium phosphate lithium/carbon composite material.
2. the method for a step sol-gal process synthesis vanadium phosphate lithium/carbon composite material according to claim 1, is characterized in that: described Li source compound is lithium dihydrogen phosphate, lithium carbonate, lithium nitrate, lithium hydroxide, lithium acetate or lithium sulfate.
3. the method for a step sol-gal process synthesis vanadium phosphate lithium/carbon composite material according to claim 1, is characterized in that: described vanadium source compound is vanadic oxide or ammonium metavanadate.
4. the method for a step sol-gal process synthesis vanadium phosphate lithium/carbon composite material according to claim 1, is characterized in that: described P source compound is lithium dihydrogen phosphate, ammonium di-hydrogen phosphate, DAP or ammonium phosphate.
5. the method for a step sol-gal process synthesis vanadium phosphate lithium/carbon composite material according to claim 1, is characterized in that: described chelating agent to be oxalic acid, citric acid or mass ratio be 30% hydrogen peroxide.
6. the method for a step sol-gal process synthesis vanadium phosphate lithium/carbon composite material according to claim 1, it is characterized in that: described carbon source is any one or more any molar mixture in acetylene black, graphite powder, superconduction carbon black, citric acid and solvable carbohydrate, wherein carbon content accounting is 3 ~ 15% of the quality of the vanadium phosphate lithium/carbon composite material generated.
7. the method for a step sol-gal process synthesis vanadium phosphate lithium/carbon composite material according to claim 1, is characterized in that: described inert gas is argon gas or nitrogen; Described reducibility gas is the mist of argon gas, CO (carbon monoxide converter) gas, nitrogen and hydrogen, and wherein hydrogen or CO (carbon monoxide converter) gas account for 2 ~ 8% of mist volume.
8. the method for a step sol-gal process synthesis vanadium phosphate lithium/carbon composite material according to claim 1, is characterized in that: the closed glass jar that described closed container is the blue bottle of silk, ground flask or adds a cover; Described heating furnace is tube furnace.
9. the method for a step sol-gal process synthesis vanadium phosphate lithium/carbon composite material according to any one of claim 1 to 8, it is characterized in that: also have the step that the solidliquid mixture that obtains after to step (1) processes further before the step (2), process refers to and adopts ultrasonic disperse, hydro-thermal, adjustment solution pH value and at least one processing method of adding in surfactant to process solidliquid mixture further.
10. the method for a step sol-gal process synthesis vanadium phosphate lithium/carbon composite material according to claim 9, is characterized in that: the processing time of described ultrasonic disperse process is 0.5 ~ 6h; The temperature of described hydrothermal treatment consists is 180 ~ 240 DEG C, and temperature retention time is 2 ~ 40h; The pH value adjustable range of described adjustment solution pH value process is 2 ~ 11; The surfactant that the process of described interpolation surfactant adopts is cetyl trimethyl quaternary ammonium bromides, cetyl trimethyl amine, hydrazine hydrate or polyethylene glycol.
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