CN101367513B - Method for preparing vanadium-lithium phosphate - Google Patents
Method for preparing vanadium-lithium phosphate Download PDFInfo
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- CN101367513B CN101367513B CN2008100461962A CN200810046196A CN101367513B CN 101367513 B CN101367513 B CN 101367513B CN 2008100461962 A CN2008100461962 A CN 2008100461962A CN 200810046196 A CN200810046196 A CN 200810046196A CN 101367513 B CN101367513 B CN 101367513B
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Abstract
The invention relates to a method for preparing the lithium vanadium phosphate, which adopts the steps: (1) preparing the precursors, in which, the raw materials include lithium, vanadium and phosphate radical, and the mol ratio among the lithium, the vanadium and the phosphate radical is 2.9 to 3.3: 2: 3, and the mol ratio between the vanadium and the carbon is 1: 1.0 to 5.5; proffers of each raw material substance according to the configuration ratio of the raw material substance are calculated, and are arranged into a reaction container and are added with water to be mixed at the normal atmosphere and the temperature of 60 to 90 DEG C, until the proffers of all raw material substances are completely dissolved, and then the obtained solution is decompressed and distilled, and the precursors are obtained after the water content is evaporated; (2) calcining, in which, under the protection of the inert gases, the precursors are heat preserved for 6 to 20 hours at the normal atmosphere and the temperature of 550 to 950 DEG C, and are cooled down to the room temperature along with the furnace, so as to get the lithium vanadium phosphate. The lithium vanadium phosphate that is prepared with the method hereinabove has high specific capacity and good cycling stability, and is suitable to be used as the anode material of the lithium-ion secondary battery.
Description
Technical field
The invention belongs to the phosphoric acid vanadium lithium field, particularly a kind of preparation method of phosphoric acid vanadium lithium.
Background technology
Lithium-ion secondary cell has characteristics such as high-voltage, heavy body, unit energy are big, safety and environmental protection, and its important component part comprises positive pole, negative pole, ionogen, barrier film, and wherein the positive electrode material development is slower, becomes the bottleneck of lithium-ion secondary cell development.Phosphoric acid vanadium lithium Li
3V
2(PO
4)
3Exist with oblique system and two kinds of forms of rhombic system.Monoclinic phosphoric acid vanadium lithium has advantages such as thermostability height, specific storage height, cyclical stability are good, the use temperature scope is wide, and having potentiality becomes s-generation phosphate radical polyanion lithium ion secondary battery anode material after LiFePO 4.
The preparation method of phosphoric acid vanadium lithium is more at present, and the difference of reductive agent can be divided into hydrogen reduction method (is reductive agent with hydrogen) and carbothermic method (is reductive agent with carbon) during according to reaction; Preparation method according to presoma can be divided into solid phase method, sol-gel method, hydrothermal method etc.Solid phase method is each raw material ball milling to be mixed back high-temperature calcination reaction make; Sol-gel method is that the raw material wiring solution-forming is mixed, and regulates pH value formation colloidal sol after drying, decomposition, ball milling, pyroreaction again; Hydrothermal method is that stoichiometric raw material and solvent are added in the autoclave, reacts to make under high-temperature and high-pressure conditions.Though solid phase method is simple to operate, the product primary particle size is bigger, and cyclical stability is relatively poor; Gel molecular is less in the sol-gel processing, and each raw material mixes fully, and the products obtained therefrom quality is higher, but the system gelation process is too loaded down with trivial details; Hydrothermal method requires reactor pressure to reach 20 more than the normal atmosphere, during industrial production facility investment big, potential safety hazard is big.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of novel phosphoric acid vanadium lithium preparation method is provided, this kind method is the quality product height not only, and technology is simple, and operational safety is convenient to suitability for industrialized production.
The preparation method of phosphoric acid vanadium lithium of the present invention, its processing step is as follows:
(1) preparation of presoma
Raw material comprises lithium, vanadium, phosphate radical and carbon, and the mol ratio of lithium, vanadium, phosphate radical is a lithium: vanadium: phosphate radical=2.9～3.3: 2: 3, the mol ratio of vanadium and carbon was a vanadium: carbon=1: 1.0～5.5;
The thing that provides of each raw material is provided by the said ratio of raw material, providing thing to put into reaction vessel and adding water and stir each raw material normal pressure, 60 ℃～90 ℃, up to each raw material provide thing to dissolve fully to form no stratified solution till (need are 3 hours at least), with the distillation of obtaining solution decompression, evaporating water promptly obtains presoma then;
(2) calcining
The prepared presoma of step (1) is put into process furnace, under protection of inert gas in normal pressure, 550 ℃～950 ℃ the insulation 6 hours～20 hours, naturally cool to room temperature with stove then, promptly obtain phosphoric acid vanadium lithium, the phosphoric acid vanadium lithium that obtains is a monoclinic form.
To calcine the phosphoric acid vanadium lithium ball milling powdering thing that obtains, select the sieve screening of different meshes as required, obtain varigrained phosphoric acid vanadium lithium powder.
For cyclical stability and the specific storage that improves phosphoric acid vanadium lithium, the present invention has taked adulterated technical scheme, promptly in the raw material of preparation presoma, increase doped element, described doped element is at least a kind of in cadmium, cerium, zirconium, aluminium, niobium, magnesium, manganese, strontium, the chromium, and the mol ratio of described doped element and lithium is a doped element: lithium=0.1～5: 100.
Raw material in the method for the invention source is wider, and thing is provided below preferred: the thing that provides of lithium is at least a kind of in Quilonum Retard, lithium hydroxide, the monometallic; The thing that provides of vanadium is ammonium meta-vanadate or Vanadium Pentoxide in FLAKES, and the thing that provides of phosphate radical is phosphoric acid or primary ammonium phosphate or monometallic; The thing that provides of carbon is a kind of in tartrate, citric acid, Whitfield's ointment, sucrose, polyoxyethylene glycol, the polystyrene.
The present invention has following beneficial effect:
1, the phosphoric acid vanadium lithium primary particle size of the method for the invention preparation is between 100～200nm, not doping phosphoric acid vanadium lithium first loading capacity be 122mA.h.g
-1, good cycling stability is fit to do lithium ion secondary battery anode material (seeing embodiment 1); Doping phosphoric acid vanadium lithium is compared with unadulterated phosphoric acid vanadium lithium, and loading capacity improves first, and cyclical stability improves (seeing embodiment 2-5).
2, the method for the invention adopts one-step calcination, and technology is simple, operates under normal pressure, and required equipment is popular response container and process furnace, thereby helps suitability for industrialized production.
Description of drawings
Fig. 1 is the X-ray diffractogram with the phosphoric acid vanadium lithium of the method for the invention preparation;
Fig. 2 is the X-ray diffractogram with the phosphoric acid vanadium lithium of the doping cadmium of the method for the invention preparation;
Fig. 3 is the X-ray diffractogram with the phosphoric acid vanadium lithium of the doped with cerium of the method for the invention preparation;
Fig. 4 is the X-ray diffractogram with the phosphoric acid vanadium lithium of the doping zirconium of the method for the invention preparation;
Fig. 5 is the X-ray diffractogram with the phosphoric acid vanadium lithium of the adulterated al of the method for the invention preparation;
Fig. 6 is the charge and discharge cycles test pattern with the phosphoric acid vanadium lithium of the method for the invention preparation;
Fig. 7 is the charge and discharge cycles test pattern with the phosphoric acid vanadium lithium of the doping cadmium of the method for the invention preparation;
Fig. 8 is the charge and discharge cycles test pattern with the phosphoric acid vanadium lithium of the doped with cerium of the method for the invention preparation;
Fig. 9 is the charge and discharge cycles test pattern with the phosphoric acid vanadium lithium of the doping zirconium of the method for the invention preparation;
Figure 10 is the charge and discharge cycles test pattern with the phosphoric acid vanadium lithium of the adulterated al of the method for the invention preparation.
Embodiment
In the present embodiment, phosphoric acid vanadium lithium preparation method's processing step is as follows:
(1) preparation of presoma
Raw material and provide thing to be:
Lithium 0.165mol (lithium hydroxide 6.9234 grams), vanadium 0.1mol (ammonium meta-vanadate 11.698 grams), phosphate radical 0.15mol (primary ammonium phosphate 17.253 grams), carbon 0.28mol (sucrose 8.1 grams);
With described proportion raw material material provide thing lithium hydroxide, ammonium meta-vanadate, primary ammonium phosphate and sucrose put into flask and add 105 the gram deionized waters, then flask is put into heating in water bath, stirred 4.5 hours at normal pressure, 60 ℃ of constant temperature, each raw material provides thing to dissolve fully and obtains not having layering solution, with obtaining solution decompression distillation (vacuum degree control-0.095MPa) evaporating water promptly obtains presoma;
(2) calcining
The presoma of step (1) preparation is put into electric tube furnace, under argon shield, be warmed up to 550 ℃ of insulations and close the tubular type furnace power after 12 hours, keep the argon atmosphere in the stove to naturally cool to room temperature, obtain the black solid product through 1 hour.The XRD analysis result of obtained product as shown in Figure 1, Fig. 1 shows that obtained product is the phosphoric acid vanadium lithium of monoclinic form.
Carbon content is analyzed:
The nitric acid dousing method is adopted in the carbon content analysis, take by weighing phosphoric acid vanadium lithium 1 gram of present embodiment preparation, add nitric acid (mass percent is 5%) and under normal pressure, room temperature, soak 3 hours (mass ratio of nitric acid and phosphoric acid vanadium lithium is 10: 1), filter with No. 4 glass sand hourglasses then, weigh after the drying wherein carbon content be 9.1%.
The charge and discharge cycles test:
Phosphoric acid vanadium lithium positive electrode material, acetylene black, polyvinylidene difluoride (PVDF) (N-Methyl pyrrolidone solution) are pressed 80: 15: 5 batchings of mass ratio, through the mixed anode sizing agent that gets of ball milling, slurry is evenly coated on the circular aluminium flake of 10 millimeters of diameters and and obtains positive pole in 110 ℃ of oven dry, described positive pole is assembled into battery with the negative pole of purchasing, ionogen, barrier film etc., carries out the charge and discharge cycles test in the 0.1C multiplying power.The result of charge and discharge cycles test as shown in Figure 6, Fig. 6 shows that loading capacity is 122mA.h.g first
-1, good cycling stability is fit to do lithium ion secondary battery anode material.
Embodiment 2
In the present embodiment, phosphoric acid vanadium lithium preparation method's processing step is as follows:
(1) preparation of presoma
Raw material and provide thing to be:
Lithium 0.15mol (lithium hydroxide 6.294 grams), vanadium 0.1mol (ammonium meta-vanadate 11.698 grams), phosphate radical 0.15mol (primary ammonium phosphate 17.253 grams), carbon 0.23mol (citric acid 8.2 grams), cadmium 0.00077mol (Cadmium oxide 0.1 gram);
With described proportion raw material material provide thing lithium hydroxide, ammonium meta-vanadate, primary ammonium phosphate, citric acid and Cadmium oxide put into flask and add 150 the gram deionized waters, then flask is put into heating in water bath, stirred 6 hours at normal pressure, 85 ℃ of constant temperature, each raw material provides thing to dissolve fully and obtains not having layering solution, with obtaining solution decompression distillation (vacuum degree control-0.09MPa), evaporating water promptly obtains presoma;
(2) calcining
The presoma of step (1) preparation is put into electric tube furnace, under nitrogen protection, be warmed up to 850 ℃ of insulations and close the tubular type furnace power after 10 hours, keep the nitrogen atmosphere in the stove to naturally cool to room temperature, obtain the black solid product through 2 hours.The XRD analysis result of obtained product as shown in Figure 2, Fig. 2 shows that the phosphoric acid vanadium lithium that obtains remains monoclinic form, illustrates that mixing cadmium can't change its crystalline structure.
Carbon content is analyzed:
Analytical procedure is identical with embodiment 1, and the carbon content of the phosphoric acid vanadium lithium of present embodiment preparation is 6.8%.
The charge and discharge cycles test:
Testing method is identical with embodiment 1, and test result is compared as can be known with Fig. 6 as shown in Figure 7, and the phosphoric acid vanadium lithium of present embodiment preparation loading capacity first improves, and cyclical stability improves, and this is owing to mix due to the cadmium.
In the present embodiment, phosphoric acid vanadium lithium preparation method's processing step is as follows:
(1) preparation of presoma
Raw material and provide thing to be:
Lithium 0.15mol (Quilonum Retard 5.5565 grams), vanadium 0.1mol (Vanadium Pentoxide in FLAKES 9.094 grams), phosphate radical 0.15mol (phosphatase 11 7.24 grams of massfraction 85.25%), carbon 0.187mol (polyoxyethylene glycol 8004.5 grams), cerium 0.00087mol (cerium oxide 0.15 gram);
With described proportion raw material material provide thing Quilonum Retard, Vanadium Pentoxide in FLAKES, phosphoric acid, polyoxyethylene glycol 800 and cerium oxide put into flask and add 18.3 the gram deionized waters, then flask is put into heating in water bath, stirred 5 hours at normal pressure, 80 ℃ of constant temperature, each raw material provides thing to dissolve fully and obtains not having layering solution, with obtaining solution decompression distillation (vacuum degree control-0.089MPa), evaporating water promptly obtains presoma;
(2) calcining
The presoma of step (1) preparation is put into electric tube furnace, under nitrogen protection, be warmed up to 800 ℃ of insulations and close the tubular type furnace power after 12 hours, keep the nitrogen atmosphere in the stove to naturally cool to room temperature, obtain the black solid product through 3.5 hours.The XRD analysis result of obtained product as shown in Figure 3, Fig. 3 shows that the phosphoric acid vanadium lithium that obtains remains monoclinic form, illustrates that mixing cerium can't change its crystalline structure.
Carbon content is analyzed:
Analytical procedure is identical with embodiment 1, and the carbon content of the phosphoric acid vanadium lithium of present embodiment preparation is 4.6%.
The charge and discharge cycles test:
Testing method is identical with embodiment 1, and test result is compared as can be known with Fig. 6 as shown in Figure 8, and the phosphoric acid vanadium lithium of present embodiment preparation loading capacity first improves, and cyclical stability improves.
Embodiment 4
In the present embodiment, phosphoric acid vanadium lithium preparation method's processing step is as follows:
(1) preparation of presoma
Raw material and provide thing to be:
Lithium 0.15mol (lithium hydroxide 6.294 grams), vanadium 0.1mol (Vanadium Pentoxide in FLAKES 9.094 grams), phosphate radical 0.15mol (phosphatase 11 7.24 grams of massfraction 85.25%), carbon 0.187mol (tartrate 7.05 grams), zirconium 0.001mol (zirconium white 0.12 gram);
With described proportion raw material material provide thing lithium hydroxide, Vanadium Pentoxide in FLAKES, phosphoric acid, tartrate and zirconium white put into flask and add 125 the gram deionized waters, then flask is put into heating in water bath, stirred 4.5 hours at normal pressure, 90 ℃ of constant temperature, each raw material provides thing to dissolve fully and obtains not having layering solution, with obtaining solution decompression distillation (vacuum degree control-0.093MPa), evaporating water promptly obtains presoma;
(2) calcining
The presoma of step (1) preparation is put into electric tube furnace, under argon shield, be warmed up to 750 ℃ of insulations and close the tubular type furnace power after 8 hours, keep the argon atmosphere in the stove to naturally cool to room temperature, obtain the black solid product through 2 hours.The XRD analysis result of obtained product as shown in Figure 4, Fig. 4 shows that the phosphoric acid vanadium lithium that obtains remains monoclinic form, illustrates that mixing zirconium can't change its crystalline structure.
Carbon content is analyzed:
Analytical procedure is identical with embodiment 1, and the carbon content of the phosphoric acid vanadium lithium of present embodiment preparation is 4.3%.
The charge and discharge cycles test:
Testing method is identical with embodiment 1, and test result is compared as can be known with Fig. 6 as shown in Figure 9, and the phosphoric acid vanadium lithium of present embodiment preparation loading capacity first improves, and cyclical stability improves.
In the present embodiment, phosphoric acid vanadium lithium preparation method's processing step is as follows:
(1) preparation of presoma
Raw material and provide thing to be:
Lithium 0.15mol (lithium hydroxide 6.294 grams), vanadium 0.1mol (Vanadium Pentoxide in FLAKES 9.094 grams), phosphate radical 0.15mol (phosphatase 11 7.24 grams of massfraction 85.25%), carbon 0.287mol (polystyrene 30 grams), aluminium 0.006mol (aluminium sesquioxide 0.3059 gram);
With described proportion raw material material provide thing lithium hydroxide, Vanadium Pentoxide in FLAKES, phosphoric acid, polystyrene and aluminium sesquioxide put into flask and add 125 the gram deionized waters, then flask is put into heating in water bath, stirred 3 hours at normal pressure, 85 ℃ of constant temperature, each raw material provides thing to dissolve fully and obtains not having layering solution, with obtaining solution decompression distillation (vacuum degree control-0.088MPa), evaporating water promptly obtains presoma;
(2) calcining
The presoma of step (1) preparation is put into electric tube furnace, under argon shield, be warmed up to 700 ℃ of insulations and close the tubular type furnace power after 20 hours, keep the argon atmosphere in the stove to naturally cool to room temperature, obtain the black solid product through 1.5 hours.The XRD analysis result of obtained product as shown in Figure 5, Fig. 5 shows that the phosphoric acid vanadium lithium that obtains remains monoclinic form, illustrates that mixing aluminium can't change its crystalline structure.
Carbon content is analyzed:
Analytical procedure is identical with embodiment 1, and the carbon content of the phosphoric acid vanadium lithium of present embodiment preparation is 9.5%.
The charge and discharge cycles test:
Testing method is identical with embodiment 1, and test result is compared as can be known with Fig. 6 as shown in figure 10, and the phosphoric acid vanadium lithium of present embodiment preparation loading capacity first improves, and cyclical stability improves.
Embodiment 6
In the present embodiment, phosphoric acid vanadium lithium preparation method's processing step is as follows:
(1) preparation of presoma
Raw material and provide thing to be:
Lithium 0.092mol (lithium hydroxide 3.8559 grams), vanadium 0.06mol (ammonium meta-vanadate 7.0897 grams), phosphate radical 0.09mol (phosphatase 11 0.3468 gram of massfraction 85.25%), carbon 0.243mol (Whitfield's ointment 4.7922 grams), niobium 0.003mol (Niobium Pentxoxide 0.3987 gram);
With described proportion raw material material provide thing lithium hydroxide, ammonium meta-vanadate, phosphoric acid, Whitfield's ointment and Niobium Pentxoxide put into flask and add 50 the gram deionized waters, then flask is put into heating in water bath, stirred 5.5 hours at normal pressure, 70 ℃ of constant temperature, each raw material provides thing to dissolve fully and obtains not having layering solution, with obtaining solution decompression distillation (vacuum degree control-0.094MPa), evaporating water promptly obtains presoma;
(2) calcining
The presoma of step (1) preparation is put into electric tube furnace, under argon shield, be warmed up to 750 ℃ of insulations and close the tubular type furnace power after 7 hours, keep the argon atmosphere in the stove to naturally cool to room temperature, obtain the black solid product through 2 hours.
Carbon content is analyzed:
Analytical procedure is identical with embodiment 1, and the carbon content of the phosphoric acid vanadium lithium of present embodiment preparation is 13.9%.
In the present embodiment, phosphoric acid vanadium lithium preparation method's processing step is as follows:
(1) preparation of presoma
Raw material and provide thing to be:
Lithium 0.087mol (Quilonum Retard 3.2191 grams), vanadium 0.06mol (Vanadium Pentoxide in FLAKES 5.46 grams), phosphate radical 0.09mol (phosphatase 11 0.3468 gram of massfraction 85.25%), carbon 0.24mol (tartrate 9.034 grams), magnesium 0.00348mol (magnesium basic carbonate 0.3501 gram), niobium 0.00087mol (Niobium Pentxoxide 0.1156 gram);
With described proportion raw material material provide thing Quilonum Retard, Vanadium Pentoxide in FLAKES, phosphoric acid, tartrate, magnesium basic carbonate and Niobium Pentxoxide put into flask and add 90 the gram deionized waters, then flask is put into heating in water bath, stirred 6.5 hours at normal pressure, 75 ℃ of constant temperature, each raw material provides thing to dissolve fully and obtains not having layering solution, with obtaining solution decompression distillation (vacuum degree control-0.088MPa), evaporating water promptly obtains presoma;
(2) calcining
The presoma of step (1) preparation is put into electric tube furnace, under argon shield, be warmed up to 900 ℃ of insulations and close the tubular type furnace power after 6 hours, keep the argon atmosphere in the stove to naturally cool to room temperature, obtain the black solid product through 2 hours.
Carbon content is analyzed:
Analytical procedure is identical with embodiment 1, and the carbon content of the phosphoric acid vanadium lithium of present embodiment preparation is 14.3%.
Embodiment 8
In the present embodiment, phosphoric acid vanadium lithium preparation method's processing step is as follows:
(1) preparation of presoma
Raw material and provide thing to be:
Lithium 0.09mol (lithium hydroxide 3.7764 grams), vanadium 0.06mol (ammonium meta-vanadate 7.0188 grams), phosphate radical 0.09mol (phosphatase 11 0.3475 gram of massfraction 85.25%), carbon 0.06mol (tartrate 2.2623 grams), manganese 0.0009mol (Manganse Dioxide 0.08 gram);
With described proportion raw material material provide thing lithium hydroxide, ammonium meta-vanadate, phosphoric acid, tartrate and Manganse Dioxide put into flask and add 100 the gram deionized waters, then flask is put into heating in water bath, stirred 3.5 hours at normal pressure, 90 ℃ of constant temperature, each raw material provides thing to dissolve fully and obtains not having layering solution, with obtaining solution decompression distillation (vacuum degree control-0.09MPa), evaporating water promptly obtains presoma;
(2) calcining
The presoma of step (1) preparation is put into electric tube furnace, under argon shield, be warmed up to 850 ℃ of insulations and close the tubular type furnace power after 8 hours, keep the argon atmosphere in the stove to naturally cool to room temperature, obtain the black solid product through 2 hours.
Carbon content is analyzed:
Analytical procedure is identical with embodiment 1, and the carbon content of the phosphoric acid vanadium lithium of present embodiment preparation is 0.6%.
(1) preparation of presoma
Raw material and provide thing to be:
Lithium 0.062mol (lithium hydroxide 2.6106 grams), lithium 0.031mol (Quilonum Retard 1.147 grams), vanadium 0.08mol (ammonium meta-vanadate 9.3588 grams), phosphate radical 0.12mol (phosphatase 11 3.7939 grams of massfraction 85.25%), carbon 0.44mol (citric acid 15.41 grams), strontium 0.00012mol (strontium hydroxide 0.032 gram);
With described proportion raw material material provide thing lithium hydroxide, Quilonum Retard, ammonium meta-vanadate, phosphoric acid, citric acid and strontium hydroxide put into flask and add 150 the gram deionized waters, then flask is put into heating in water bath, stirred 5.5 hours at normal pressure, 85 ℃ of constant temperature, each raw material provides thing to dissolve fully and obtains not having layering solution, with obtaining solution decompression distillation (vacuum degree control-0.093MPa), evaporating water promptly obtains presoma;
(2) calcining
The presoma of step (1) preparation is put into electric tube furnace, under argon shield, be warmed up to 950 ℃ of insulations and close the tubular type furnace power after 10 hours, keep the argon atmosphere in the stove to naturally cool to room temperature, obtain the black solid product through 4.5 hours.
Carbon content is analyzed:
Analytical procedure is identical with embodiment 1, and the carbon content of the phosphoric acid vanadium lithium of present embodiment preparation is 18.3%.
(1) preparation of presoma
Raw material and provide thing to be:
Lithium 0.3mol and phosphate radical 0.3mol (monometallic 31.179 grams), vanadium 0.2mol (Vanadium Pentoxide in FLAKES 18.2 grams), carbon 0.57mol (citric acid 20 grams), chromium 0.0015mol (chromium sesquioxide 0.228 gram);
With described proportion raw material material provide thing monometallic, Vanadium Pentoxide in FLAKES, citric acid and chromium sesquioxide put into flask and add 452.5 the gram deionized waters, then flask is put into heating in water bath, stirred 6.5 hours at normal pressure, 65 ℃ of constant temperature, each raw material provides thing to dissolve fully and obtains not having layering solution, with obtaining solution decompression distillation (vacuum degree control-0.09MPa), evaporating water promptly obtains presoma;
(2) calcining
The presoma of step (1) preparation is put into electric tube furnace, under argon shield, be warmed up to 650 ℃ of insulations and close the tubular type furnace power after 15 hours, keep the argon atmosphere in the stove to naturally cool to room temperature, obtain the black solid product through 2 hours.
Carbon content is analyzed:
Analytical procedure is identical with embodiment 1, and the carbon content of the phosphoric acid vanadium lithium of present embodiment preparation is 9.3%.
Claims (3)
1. the preparation method of a phosphoric acid vanadium lithium is characterized in that processing step is as follows:
(1) preparation of presoma
Raw material comprises lithium, vanadium, phosphate radical and carbon, and the mol ratio of lithium, vanadium, phosphate radical is a lithium: vanadium: phosphate radical=2.9～3.3: 2: 3, the mol ratio of vanadium and carbon was a vanadium: carbon=1: 1.87～5.5;
The thing that provides of each raw material is provided by the said ratio of raw material, providing thing to put into reaction vessel and adding water and stir each raw material normal pressure, 60 ℃～90 ℃, up to each raw material provide thing to dissolve fully to form no stratified solution till, with the distillation of obtaining solution decompression, evaporating water promptly obtains presoma then;
(2) calcining
The prepared presoma of step (1) is put into process furnace, under protection of inert gas in normal pressure, 550 ℃～950 ℃ the insulation 6 hours～20 hours, naturally cool to room temperature with stove then, promptly obtain phosphoric acid vanadium lithium.
2. the preparation method of phosphoric acid vanadium lithium according to claim 1, the raw material that it is characterized in that the presoma preparation process also comprises doped element, described doped element is at least a kind of in cadmium, cerium, zirconium, aluminium, niobium, magnesium, manganese, strontium, the chromium, and the mol ratio of described doped element and lithium is a doped element: lithium=0.1～5: 100.
3. the preparation method of phosphoric acid vanadium lithium according to claim 1 and 2, the thing that provides that it is characterized in that lithium is at least a kind of in Quilonum Retard, lithium hydroxide, the monometallic, the thing that provides of vanadium is ammonium meta-vanadate or Vanadium Pentoxide in FLAKES, the thing that provides of phosphate radical is phosphoric acid or primary ammonium phosphate or monometallic, and the thing that provides of carbon is a kind of in tartrate, citric acid, Whitfield's ointment, sucrose, polyoxyethylene glycol, the polystyrene.
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| CN102234101B (en) * | 2010-04-26 | 2014-04-30 | 深圳市比克电池有限公司 | Micron nano structure Li3V2(PO4)3/C compound as well as preparation method and application thereof |
| CN101841027A (en) * | 2010-05-13 | 2010-09-22 | 湘西自治州矿产与新材料技术创新服务中心 | Method for preparing lithium position rare earth-doped lithium vanadyl phosphate cathode material for lithium ion battery |
| CN102496718A (en) * | 2011-12-29 | 2012-06-13 | 哈尔滨工业大学 | Preparation method of lithium ion battery anode material Li3V2(PO4)3 |
| CN102774821B (en) * | 2012-07-30 | 2014-05-21 | 四川大学 | Solid phase-hydrothermal preparation method for lithium vanadium phosphate |
| PL436667A1 (en) * | 2018-06-30 | 2022-01-10 | Attia Mai | Method for removing cadmium and other metals and impurities from materials containing phosphates |
| CN113699687B (en) * | 2021-08-18 | 2022-08-05 | 三峡大学 | Double-needle electrostatic spinning Li 3 VO 4 Preparation method of/C fiber lithium ion battery cathode material |
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