CN108285133A - Phosphoric acid vanadium lithium and preparation method thereof - Google Patents
Phosphoric acid vanadium lithium and preparation method thereof Download PDFInfo
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- CN108285133A CN108285133A CN201810072000.0A CN201810072000A CN108285133A CN 108285133 A CN108285133 A CN 108285133A CN 201810072000 A CN201810072000 A CN 201810072000A CN 108285133 A CN108285133 A CN 108285133A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of preparation methods of phosphoric acid vanadium lithium, include the following steps：Lithium source, vanadium source, phosphorus source are provided, first the lithium source is dissolved in inorganic acid, the vanadium source, phosphorus source, complexing agent mixing is then added, precursor solution is obtained by the reaction under conditions of temperature is less than 0 DEG C；The precursor solution is subjected to vacuum drying treatment under conditions of less than 0 DEG C, obtains phosphoric acid vanadium lithium presoma；The phosphoric acid vanadium lithium presoma is subjected to the first sintering processes, the second sintering processes successively, obtains phosphoric acid vanadium lithium, wherein second sintering processes carry out in an inert atmosphere.
Description
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of phosphoric acid vanadium lithium and preparation method thereof.
Background technology
In recent years, phosphoric acid vanadium lithium is due to high-lithium ion diffuser efficiency, higher discharge capacity and energy density, and has
Good cycle performance and thermal stability, get more and more people's extensive concerning.In addition, phosphoric acid vanadium lithium has three-dimensional lithium ion diffusion
Channel, compared with the LiFePO4 of one-dimensional ion diffusion admittance, high rate performance is improved significantly.Therefore, lithium vanadium phosphate material
It is high development energy density, high rate performance and one of the preferred positive electrode of lithium-ion-power cell having a safety feature.
Research shows that：Granule-morphology has tremendous influence, the vanadium phosphate that particle is uniform, tiny to lithium vanadium phosphate material performance
Lithium material has larger specific surface area, can improve its chemical property.Currently, the synthetic method of lithium vanadium phosphate material has very
It is more, including solid-phase synthesis and liquid phase synthesizing method.Wherein, the method for solid-phase synthesis is usually：The atomic molar of phosphoric acid vanadium lithium
Than lithium carbonate, metavanadic acid are pressed, ammonium dihydrogen phosphate grinding it is uniform, be placed in tube furnace and be heated to 350 DEG C, keep the temperature 2h, obtain
Blocky blackish green presoma；Then 10% carbon source is added, then this presoma is ground to powder, is placed in tube furnace, 800 degree of sintering
8h obtains black powder.By four probe tests, the lithium vanadium phosphate material powder resistance rate prepared by the method is smaller,
For 4 Europe centimetre.But solid-phase synthesis belongs to physical mixed, and mixability is extremely uneven, or even is easy part and reunites.Currently, liquid
Phase synthesi substantially flow is：Take lithium source, vanadium source, phosphorus source, complexing agent, dispersant soluble in water, 100 DEG C of stirring 2h are precipitated molten
Solution obtains precursor solution, and drying and processing prepares presoma；It is sintered the presoma to obtain phosphoric acid vanadium lithium.But it should
Phosphoric acid vanadium lithium prepared by method leads to lithium source, vanadium source, phosphorus source etc. since dissolution dispersity can be poor in precursor solution for lithium source
It is poor to disperse uneven, prepared phosphoric acid vanadium lithium chemical property.
Invention content
The purpose of the present invention is to provide a kind of phosphoric acid vanadium lithiums and preparation method thereof, it is intended to solve the phosphorus of existing method preparation
Sour vanadium lithium, the dispersion such as lithium source, vanadium source, phosphorus source is uneven, leads to the problem of preparation-obtained phosphoric acid vanadium lithium chemical property difference.
For achieving the above object, the technical solution adopted by the present invention is as follows：
One aspect of the present invention provides a kind of preparation method of phosphoric acid vanadium lithium, includes the following steps：
Lithium source, vanadium source, phosphorus source are provided, first the lithium source is dissolved in inorganic acid, the vanadium source, phosphorus source, network is then added
Mixture mixes, and precursor solution is obtained by the reaction under conditions of temperature is less than 100 DEG C；
The precursor solution is subjected to vacuum drying treatment under conditions of less than 0 DEG C, obtains phosphoric acid vanadium lithium presoma；
The phosphoric acid vanadium lithium presoma is subjected to the first sintering processes, the second sintering processes successively, obtains phosphoric acid vanadium lithium,
In, second sintering processes carry out in an inert atmosphere.
Preferably, the lithium source is lithium carbonate, and the inorganic acid is nitric acid.
Preferably, the nitric acid is selected from the nitric acid that mass percentage concentration is 68%.
Preferably, the vacuum drying treatment is freeze-drying process.
Preferably, in the step of phosphoric acid vanadium lithium presoma being carried out the first sintering processes, the second sintering processes successively,
By the gaseous environment after first sintering processes into line replacement, it is replaced as inert gas, makes second sintering processes lazy
It is carried out in property atmosphere.
Preferably, the temperature of first sintering processes is 300-400 DEG C, time 3-5h；
The temperature of second sintering processes is 700-900 DEG C, time 6-12h.
Preferably, the complexing agent is organic acid.
Preferably, the complexing agent is selected from least one of citric acid, oxalic acid.
Preferably, the lithium source is dissolved in the step in inorganic acid, the molar ratio of the inorganic acid and lithium source is 1.3-
2.5：1.
And a kind of phosphoric acid vanadium lithium, the phosphoric acid vanadium lithium are prepared by the above method.
The preparation method of phosphoric acid vanadium lithium provided by the invention, has the following advantages：
First, on the one hand, solvent soln of the inorganic acid as precursor solution is used, it can not only preferably dissolving lithium
Source, vanadium source, phosphorus source；It, can be to avoid generating into influence during the reaction moreover, replace water as dissolution solvent using inorganic acid
The substance (hydrogen that such as water generates in the reaction) of chemical property introduces not eliminable ion, improves the purity and matter of product
Amount.On the other hand, first the lithium source is dissolved in after forming evenly dispersed lithium ion in inorganic acid, adds the vanadium source, phosphorus
It is evenly dispersed in presoma to be conducive to lithium ion for source, complexing agent.Specifically, due to the property of lithium source material itself, with institute
When stating vanadium source, phosphorus source while being dissolved in inorganic acid, the vanadium source, phosphorus source can be better than the lithium source and consume acid solution, be unfavorable for lithium source
Dissolving dispersion, cause finally obtained phosphoric acid vanadium lithium crystal form unstable.And realize lithium source by increasing the content of inorganic acid
Dissolving dispersion, and the water content in the mixed solution that can be improved, the performance of the phosphoric acid vanadium lithium influenced.In addition, first
After the lithium source is dissolved in inorganic acid, add the vanadium source, phosphorus source, complexing agent addition manner, can not in addition plus
Under the premise of entering dispersant, uniform precursor solution is obtained, to avoid the impurity element introduced, is influenced in sintering process
Phosphoric acid vanadium lithium purity and the growth of phosphoric acid vanadium lithium structure cell, phosphoric acid vanadium lithium pattern, and then influence the chemical property of phosphoric acid vanadium lithium.
Secondly, the present invention by the precursor solution use low-temperature vacuum drying, so as to get phosphoric acid vanadium lithium forerunner's soma
It not will produce other miscellaneous by-products during dry not only, but also ensure that phosphoric acid vanadium lithium presoma sintering pre-structure is stablized, be not easy to collapse
It falls into, to advantageously form the good phosphoric acid vanadium lithium crystal form of pattern, obtains the lithium vanadium phosphate material of chemical property raising；In addition,
During low-temperature vacuum drying, presoma and being not easy is aoxidized, and (material lithium vanadium phosphate is not oxidizable under vacuum condition, can avoid phosphorus
Sour vanadium lithia turns to unwanted vanadyl phosphate lithium).
Again, the second sintering processes of the present invention carry out in an inert atmosphere, and first sintering can be prevented processed
Some byproduct gas are generated in journey, and (such as by-product oxidizing gas can be caused to pass through the phosphoric acid vanadium lithium of the first sintering processes
Presoma generates vanadyl phosphate lithium or byproduct hydrogen gas during the second sintering processes, easily causes phosphoric acid vanadium lithium and initially compares
The reduction of capacity, while increasing loop attenuation), influence the purity and chemical property of phosphoric acid vanadium lithium.
Phosphoric acid vanadium lithium provided by the invention, is prepared using the above method, obtained phosphoric acid vanadium lithium not only particle diameter distribution
It is narrow, and there is excellent chemical property.
Description of the drawings
Fig. 1 is the charging gram volume design sketch for the phosphoric acid vanadium lithium that the embodiment of the present invention 1 provides；
Fig. 2 is the charging gram volume design sketch for the phosphoric acid vanadium lithium that comparative example 1 of the present invention provides；
Fig. 3 is the size distribution design sketch for the phosphoric acid vanadium lithium that the embodiment of the present invention 1 provides.
Specific implementation mode
In order to make technical problems, technical solutions and advantageous effects to be solved by the present invention be more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indicating or implies relative importance or implicitly indicate the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more this feature.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
An embodiment of the present invention provides a kind of preparation methods of phosphoric acid vanadium lithium, include the following steps：
S01., lithium source, vanadium source, phosphorus source are provided, first the lithium source is dissolved in inorganic acid, the vanadium source, phosphorus is then added
Source, complexing agent mixing, precursor solution is obtained by the reaction under conditions of temperature is less than 100 DEG C；
S02. the precursor solution is subjected to vacuum drying treatment under conditions of less than 0 DEG C, before obtaining phosphoric acid vanadium lithium
Drive body；
S03. the phosphoric acid vanadium lithium presoma is subjected to the first sintering processes, the second sintering processes successively, obtains vanadium phosphate
Lithium, wherein second sintering processes carry out in an inert atmosphere.
The preparation method of phosphoric acid vanadium lithium provided in an embodiment of the present invention, has the following advantages：
First, on the one hand, solvent soln of the inorganic acid as precursor solution is used, it can not only preferably dissolving lithium
Source, vanadium source, phosphorus source；It, can be to avoid generating into influence during the reaction moreover, replace water as dissolution solvent using inorganic acid
The substance (hydrogen that such as water generates in the reaction) of chemical property introduces not eliminable ion, improves the purity and matter of product
Amount.On the other hand, first the lithium source is dissolved in after forming evenly dispersed lithium ion in inorganic acid, adds the vanadium source, phosphorus
It is evenly dispersed in presoma to be conducive to lithium ion for source, complexing agent.Specifically, due to the property of lithium source material itself, with institute
When stating vanadium source, phosphorus source while being dissolved in inorganic acid, the vanadium source, phosphorus source can be better than the lithium source and consume acid solution, be unfavorable for lithium source
Dissolving dispersion, cause finally obtained phosphoric acid vanadium lithium crystal form unstable.And realize lithium source by increasing the content of inorganic acid
Dissolving dispersion, and the water content in the mixed solution that can be improved, the performance of the phosphoric acid vanadium lithium influenced.In addition, first
After the lithium source is dissolved in inorganic acid, add the vanadium source, phosphorus source, complexing agent addition manner, can not in addition plus
Under the premise of entering dispersant, uniform precursor solution is obtained, to avoid the impurity element introduced, is influenced in sintering process
Phosphoric acid vanadium lithium purity and phosphoric acid vanadium lithium structure cell grow and then influence the chemical property of phosphoric acid vanadium lithium.
Secondly, the embodiment of the present invention by the precursor solution use low-temperature vacuum drying, so as to get phosphoric acid vanadium lithium before
Other miscellaneous by-products are not will produce during drive soma is dry, sintering pre-structure is more stable, is not easy to collapse；And it is not easy to be aoxidized
(material lithium vanadium phosphate is not oxidizable under vacuum condition, and avoidable phosphoric acid vanadium lithium is oxidized to unwanted vanadyl phosphate lithium).
Again, the second sintering processes described in the embodiment of the present invention carry out in an inert atmosphere, can prevent from burning for the first time
Some byproduct gas are generated in knot processing procedure, and (such as by-product oxidizing gas can be caused to pass through the first sintering processes
Phosphoric acid vanadium lithium presoma generates vanadyl phosphate lithium or byproduct hydrogen gas during the second sintering processes, easily causes vanadium phosphate
The reduction of lithium initial specific capacities, while increasing loop attenuation), influence the purity and chemical property of phosphoric acid vanadium lithium.
Specifically, in above-mentioned steps S01, provide lithium source, vanadium source, phosphorus source, the lithium source, vanadium source, phosphorus source mole can
By phosphoric acid vanadium lithium Li3V2(PO4)3Stoichiometric ratio with reference to provide, as in lithium source, vanadium source, phosphorus source lithium, vanadium, phosphorus atom rub
You preferably satisfy 3 by content ratio:2:3, certainly, on this basis, adjustment appropriate can be carried out.
Be different from it is conventional lithium source, vanadium source, phosphorus source are mixed together dissolving after reaction prepare the mode of precursor solution, this
In inventive embodiments, first the lithium source is dissolved in inorganic acid, the vanadium source, phosphorus source, complexing agent mixing is then added.Pass through this
Kind mode, lithium source first form lithium ion, are then better dispersed in by ionic species and are formed with vanadium source, phosphorus source in mineral acid
Mixed solution in, be conducive to the evenly dispersed of lithium ion, need not the uniform of lithium ion additionally be realized using ball-milling technology
Dispersion.Further, the solvent soln using inorganic acid as precursor solution, not only to lithium source, vanadium source, phosphorus source solubility property
It is good, and the impurity introduced is few, and side reaction is few.It, can be to avoid reacting in addition, replace water as dissolution solvent using inorganic acid
The substance (hydrogen that such as water generates in the reaction) for influencing chemical property is generated into the process or introduces not eliminable ion, is carried
The purity and quality of high product.In addition, after first the lithium source is dissolved in inorganic acid, the vanadium source, phosphorus source, complexing agent are added
Addition manner, uniform precursor solution can be obtained under the premise of not additionally incorporating dispersant, to avoid introduce
Impurity element influences phosphoric acid vanadium lithium purity and the growth of phosphoric acid vanadium lithium structure cell, phosphoric acid vanadium lithium pattern in sintering process, and then influences
The chemical property of phosphoric acid vanadium lithium.
In the embodiment of the present invention, common vanadium source, phosphorus source may be used in the vanadium source, phosphorus source, wherein the vanadium source includes
But it is not limited to ammonium metavanadate, vanadic anhydride, phosphorus source includes but not limited to phosphoric acid, dihydrogen phosphate.
Preferably, the lithium source is lithium carbonate, and the inorganic acid is nitric acid.Using lithium carbonate as lithium source, use simultaneously
Nitric acid not only has excellent solubility property as inorganic acid solution lithium source, and the lithium ion advantageously formed is evenly dispersed, and
Lithium carbonate will not form lithium hydroxide during the reaction, and then introduce hydroxide ion impurity (other acid appearances for being difficult to remove
Easily cause miscellaneous side reaction, as in sulfuric acid, hydrochloric acid sulfate ion and chlorion can easily cause precipitation).It is further preferred that
The nitric acid is selected from the nitric acid that mass percentage concentration is 68%.If the concentration of nitric acid is too high, reaction is too violent, and heat release is too high,
It is unfavorable for post-processing；If the concentration of nitric acid is too low, on the one hand, be unfavorable for the lithium source and fully dissolve；On the other hand, can increase
The nitric acid usage amount is added to influence post-processing to bring excessive moisture into.
In the embodiment of the present invention, complexing agent is added in the mixed solution that lithium source, vanadium source, phosphorus source are formed.Preferably, described
Complexing agent is organic acid.Preferably, the complexing agent is selected from least one of citric acid, oxalic acid, more preferably citric acid.When
It is stronger with the chelation of phosphoric acid vanadium lithium when the complexing agent is citric acid, to obtain the more stable phosphoric acid vanadium lithium of performance
Material.
Preferably, the lithium source is dissolved in the step in inorganic acid, the molar ratio of the inorganic acid and lithium source is 1.3-
2.5：1.If the inorganic acid is inadequate, it cannot be guaranteed that lithium source dissolving is abundant, it is intact that the molding of phosphoric acid vanadium lithium crystal form can be influenced.
If the inorganic acid is too many, the dosage of the inorganic acid increases, and the moisture of institute's band also increases, and influences to detain capacitance；Meanwhile instead
Nitrogen oxides increases during answering, and chemical property is low.
The mixed solution that lithium source, vanadium source, phosphorus source are formed carries out addition reaction, and the reaction is less than 100 DEG C of item in temperature
It is carried out under part.If reaction temperature is too high, material can be caused to form certain crystalline form in presoma formation stages, post-processing can be influenced
Phosphoric acid vanadium lithium crystal form in the process, and then influence the chemical property of material.
In above-mentioned steps S02, by it is described state precursor solution carry out vacuum drying treatment, under conditions of less than 0 DEG C into
Row.The present invention by the precursor solution use low-temperature vacuum drying, so as to get phosphoric acid vanadium lithium presoma not will produce not only
Other miscellaneous by-products, and ensure that phosphoric acid vanadium lithium presoma sintering pre-structure is stablized, it is not easy to collapse, to advantageously form pattern
Good phosphoric acid vanadium lithium crystal form obtains the lithium vanadium phosphate material of chemical property raising；In addition, during low-temperature vacuum drying, it is preceding
It drives body and is not easy to be aoxidized that (material lithium vanadium phosphate is not oxidizable under vacuum condition, can avoid phosphoric acid vanadium lithium (LVP) and be oxidized to not needing
Vanadyl phosphate lithium).In the embodiment of the present invention, preferably -80 DEG C of the drying temperature~0 DEG C, more preferably -60 DEG C~-20
DEG C, it can better ensure that the stability of phosphoric acid vanadium lithium precursor construction.Preferably, the vacuum drying treatment is freeze-drying
Processing, drying temperature are -40 DEG C~-60 DEG C.The Nomenclature Composition and Structure of Complexes that presoma can be effectively ensured using vacuum drying treatment is steady
It is qualitative, be conducive to obtain the high phosphoric acid vanadium lithium of stable structure, purity.
In above-mentioned steps S03, the phosphoric acid vanadium lithium presoma is sintered, phosphoric acid vanadium lithium is prepared.The sintering
Processing includes the first sintering processes and the second sintering processes, and first sintering processes can remove volatile ingredient, that is, prepare molten
Sour gas etc. extra in presoma in liquid, second sintering processes are used to form effective phosphoric acid vanadium lithium crystalline form.
Preferably, the temperature of first sintering processes is 300-400 DEG C, time 3-5h；Second sintering processes
Temperature be 700-900 DEG C, time 6-12h.
Second sintering processes described in the embodiment of the present invention carry out in an inert atmosphere, and first sintering can be prevented processed
Some byproduct gas are generated in journey, and (such as by-product oxidizing gas can be caused to pass through the phosphoric acid vanadium lithium of the first sintering processes
Presoma produces vanadyl phosphate lithium or byproduct hydrogen gas during the second sintering processes, easily causes phosphoric acid vanadium lithium and initially compares
The reduction of capacity, while increasing loop attenuation), influence the purity and chemical property of phosphoric acid vanadium lithium.It is further preferred that will
The phosphoric acid vanadium lithium presoma was carried out successively in the step of the first sintering processes, the second sintering processes, at first sintering
Gaseous environment after reason is replaced as inert gas into line replacement, and second sintering processes is made to carry out in an inert atmosphere.
And an embodiment of the present invention provides a kind of phosphoric acid vanadium lithium, the phosphoric acid vanadium lithium is prepared by the above method.
Phosphoric acid vanadium lithium provided in an embodiment of the present invention, is prepared using the above method, obtained phosphoric acid vanadium lithium not only grain
Diameter narrowly distributing, and there is excellent chemical property.
It is illustrated with reference to specific embodiment.
Embodiment 1
A kind of preparation method of phosphoric acid vanadium lithium, includes the following steps：
It weighs lithium hydroxide and is dissolved in nitric acid and dissolve, add vanadic anhydride, dihydrogen phosphate and citric acid, (lithium
Source：Vanadium source：Phosphorus source is 1.08：1：1) it is stirred at being 70 DEG C in temperature, carries out (- 40 DEG C) vacuum drying of low temperature, obtain vanadium phosphate
Lithium presoma.Phosphoric acid vanadium lithium presoma is pre-sintered, is first warming up to 350 DEG C with the rate of 5 DEG C/min, is sintered 4h, is utilized
Nitrogen carries out a gas displacement to reative cell, then is warming up to 800 DEG C with rate for 10 DEG C/min, is sintered 10h.
Comparative example 1
A kind of preparation method of phosphoric acid vanadium lithium, includes the following steps：
By lithium carbonate, vanadic anhydride and ammonium dihydrogen phosphate according to the amount of the substance of lithium, vanadium and phosphorus ratio be 3:2:3 ratio
Example mixing is added acetone and stirs 2-5h, then carries out ball milling mixing 3-5h, after drying 4-10h, is sintered under inert gas protection
19-27h obtains phosphoric acid vanadium lithium.
The electric data of charging gram volume and button for the phosphoric acid vanadium lithium that detection embodiment 1, comparative example 1 obtain, wherein charging gram is held
The detection method of amount is：
A certain amount of NMP is taken in beaker, according to NMP：Conductive carbon：PVDF ratios are 1000：16.7：30, wait for conductive carbon
Substantially after being infiltrated by NMP, mixed solution is stirred into 2h, stirring finishes, and solution is inverted port grinding bottle, is placed in drying tower and preserves.
Material is subjected to vacuum bakeout 12h under the conditions of 100 DEG C, removes moisture.Ball grinder is cleaned out, drying is kept, it is accurate successively
It gets 10g materials, 15.6g conducting resinls and the agate bead centainly expected ready, in the ball mill after the nearly 45min of ball milling, is coated, roll-in
Processing makes pole piece.Button cell is made in cathode lithium piece and positive electrode.
The button cell prepared is tested, the detection method for detaining electric data is：By 0.2C, 0.5C, 1.0C fills
Spark gap inspection material electrochemical performance, 0.2C charging capacity 208.6mAh/g, discharge capacity 178.9mAh/g, 0.5C charging capacity
189.7mAh/g, discharge capacity 172.5mAh/g, 1.0C charging capacity 181.9mAh/g, discharge capacity 166.2mAh/g.Wherein,
The charging gram volume design sketch for the phosphoric acid vanadium lithium that the embodiment of the present invention 1 obtains is as shown in Figure 1, the phosphoric acid vanadium lithium that comparative example 1 obtains
Charging gram volume design sketch as shown in Fig. 2, the size distribution design sketch for the phosphoric acid vanadium lithium that embodiment 1 obtains is as shown in Figure 3.
Phosphoric acid vanadium lithium prepared by the embodiment of the present invention first dissolves lithium salts using specific solvent, adds other raw materials
Presoma is prepared, is sintered and obtains after freeze-dried.On the one hand, it first passes through inorganic acid and individually dissolves lithium salts, lithium salts can be improved
Dissolution dispersity；On the other hand, since the vanadium in phosphoric acid vanadium lithium is oxidized easily, the embodiment of the present invention is using at freeze-drying
Reason, makes material in a relatively low state, it is not easy to be aoxidized so that material keeps uniform state, forms stable structure
Presoma.The phosphoric acid vanadium lithium as it can be seen that prepared by the embodiment of the present invention is compared in conjunction with Fig. 1, Fig. 2, waits the charging gram under voltage conditions
Capacity is apparently higher than the phosphoric acid vanadium lithium of comparative example preparation.As seen from Figure 3, the phosphoric acid vanadium lithium grain size prepared by the embodiment of the present invention point
Cloth is narrow, has excellent chemical property.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (10)
1. a kind of preparation method of phosphoric acid vanadium lithium, which is characterized in that include the following steps：
Lithium source, vanadium source, phosphorus source are provided, first the lithium source is dissolved in inorganic acid, the vanadium source, phosphorus source, complexing agent is then added
Precursor solution is obtained by the reaction under conditions of temperature is less than 100 DEG C in mixing；
The precursor solution is subjected to vacuum drying treatment under conditions of less than 0 DEG C, obtains phosphoric acid vanadium lithium presoma；
The phosphoric acid vanadium lithium presoma is subjected to the first sintering processes, the second sintering processes successively, obtains phosphoric acid vanadium lithium, wherein
Second sintering processes carry out in an inert atmosphere.
2. the preparation method of phosphoric acid vanadium lithium as described in claim 1, which is characterized in that the lithium source is lithium carbonate, the nothing
Machine acid is nitric acid.
3. the preparation method of phosphoric acid vanadium lithium as described in claim 1, which is characterized in that the nitric acid is selected from mass percentage concentration
For 68% nitric acid.
4. the preparation method of phosphoric acid vanadium lithium as described in any one of claims 1-3, which is characterized in that the vacuum drying treatment
For freeze-drying process.
5. the preparation method of phosphoric acid vanadium lithium as described in any one of claims 1-3, which is characterized in that before the phosphoric acid vanadium lithium
It drives in the step of body carries out the first sintering processes, the second sintering processes successively, by the gaseous environment after first sintering processes
Into line replacement, it is replaced as inert gas, second sintering processes is made to carry out in an inert atmosphere.
6. the preparation method of phosphoric acid vanadium lithium as described in any one of claims 1-3, which is characterized in that first sintering processes
Temperature be 300-400 DEG C, time 3-5h；
The temperature of second sintering processes is 700-900 DEG C, time 6-12h.
7. the preparation method of phosphoric acid vanadium lithium as described in any one of claims 1-3, which is characterized in that the complexing agent is organic
Acid.
8. the preparation method of phosphoric acid vanadium lithium as claimed in claim 7, which is characterized in that the complexing agent is selected from citric acid, grass
At least one of acid.
9. the preparation method of phosphoric acid vanadium lithium as described in any one of claims 1-3, which is characterized in that the lithium source is dissolved in nothing
In step in machine acid, the molar ratio of the inorganic acid and lithium source is 1.3-2.5：1.
10. a kind of phosphoric acid vanadium lithium, which is characterized in that the phosphoric acid vanadium lithium is obtained by the preparation of any one of claim 1-9 the methods
.
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|---|---|---|---|---|
| CN110504422A (en) * | 2019-07-29 | 2019-11-26 | 全球能源互联网研究院有限公司 | A kind of cell positive material and preparation method thereof |
| CN112117433A (en) * | 2020-09-01 | 2020-12-22 | 深圳市德方纳米科技股份有限公司 | Preparation method of lithium ferrite |
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| CN112117433A (en) * | 2020-09-01 | 2020-12-22 | 深圳市德方纳米科技股份有限公司 | Preparation method of lithium ferrite |
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