CN108002356A - δ-VOPO4Ultrathin nanometer piece and its controllable method for preparing and application - Google Patents
δ-VOPO4Ultrathin nanometer piece and its controllable method for preparing and application Download PDFInfo
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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
- C01B25/37—Phosphates of heavy metals
- C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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 relates to δ VOPO4Ultrathin nanometer sheet material and its controllable method for preparing, the material can be used as anode active material of lithium ion battery, it is orthohormbic structure, thing phase and the δ VOPO that card number is 00 047 09514Standard sample fits like a glove, space group P42/ mbc, no dephasign peak, has crystallinity.The beneficial effects of the invention are as follows:δ VOPO are prepared for by simple and practicable sol-gal process combination solid sintering technology4Nanometer sheet positive electrode, when it is as anode active material of lithium ion battery, the characteristics of showing power high, good cycling stability;Secondly, present invention process is simple, by simple and practicable sol-gal process i.e. can obtain precursor solution, solution is dried and air atmosphere under solid-phase sintering can obtain δ VOPO4Nanometer sheet positive electrode.This method feasibility is strong, the characteristics of being easy to amplificationization, meet Green Chemistry, is promoted beneficial to the marketization.
Description
Technical field
The invention belongs to nanometer material and electrochemical technology field, and in particular to δ-VOPO4Ultrathin nanometer sheet material and its
Controllable method for preparing, the material can be used as anode active material of lithium ion battery.
Background technology
Since modern age, social productive forces are continuously improved with the promotion of process of industrialization, and scientific and technological progress each time is all
With the revolution in terms of using energy source.How to realize that the utilization of clean energy resource have become global research hotspot,
And the storage of clean energy resource is to influence clean energy resource to develop the most key key element.By the development of more than 20 years, lithium ion battery
Market scale is from scratch, it is contemplated that will surmount lead-acid battery before and after 2022 and is produced as the secondary cell of market dosage maximum
Product.But the fast development of pure electric automobile and hybrid vehicle proposes higher to new anode material for lithium-ion batteries
It is required that.
In many positive electrodes, VOPO4Because its discharge potential height is (close to 4V vs.Li/Li+), discharge capacity it is high
The advantages that (166mAh/g) and be considered as one of anode material for lithium-ion batteries of most potential application.It is more as a kind of homogeneity
Crystallization compound, VOPO4Due to VO6Octahedra and PO4The arrangement mode of tetrahedron element is different and existing has open three-dimensional tunnel
β, ε phase of structure and the α with two-dimensional layered structureⅠ、αⅡ, ω, δ and γ phase.Compared with other structures, δ-VOPO4In low current
There is highest discharge capacity, and discharge platform is 3.8V under density.The researchers such as B.M.Azmi also found δ-VOPO4In low power
Possess good cycle performance under rate, there is potential application prospect.But current result of study shows, δ-VOPO4Electrode
The high rate performance of material is poor, and cycle performance is remarkably decreased at higher current densities, this all have impact on its practical application valency
Value.
Result of study shows to regulate and control the structure and pattern of material by optimum synthesis method and condition and will significantly carry
High VOPO4The chemical property of positive electrode.Nanometer chip architecture can effectively shorten the diffusion path of lithium ion, alleviate lithium ion
Caused stress during deintercalation, while absorption of the nanometer sheet surface to lithium ion can improve its fake capacitance behavior, finally may be used
Significantly improve the electro-chemical activity of material.2016, Guihua Yu seminars were in aqueous isopropanol to VOPO4·H2O blocks
Carry out ultrasound stripping and be prepared for VOPO4·H2O nanometer sheets, the material show excellent when as lithium ion anode material.In 5C electricity
The discharge capacity of material is 100mAh/g under current density, and circulate 500 times after capacity it is almost undamped, be much better than block material
Material.2017, the seminar by organic matter TEG and THF by introducing VOPO4·H2The mode of O interlayers realizes VOPO4·H2O
The successful stripping of block structure, the successful insertion of organic molecule make VOPO4·H2The interlamellar spacing of O is improved, while organic molecule
With VOPO4·H2Chemical bond between O agent structures maintains stable structure of the agent structure during Lithium-ion embeding abjection
Property, finally effectively increases the high rate performance and cyclical stability of material.
However, VOPO is prepared at present4Nanometer sheet is generally peeled off using the ultrasound in aqueous isopropanol or organic matter insertion
Mode obtain, its preparation efficiency is low, of high cost, have impact on application of the material in actual production, and for δ-VOPO4Receive
The research of rice piece has not been reported.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of δ-VOPO for the above-mentioned prior art4Nanometer sheet cathode
Material and preparation method thereof, its preparation method technique is simple, meets the requirement of Green Chemistry and is easy to amplificationization, basic herein
On, δ-VOPO4Nanometer sheet positive electrode also has excellent chemical property.
Technical solution is used by the present invention solves above-mentioned technical problem:δ-VOPO4Ultrathin nanometer piece, it is positive knot
Structure, thing phase and the δ-VOPO that card number is 00-047-09514Standard sample fit like a glove ( α=90 °, β=90 °, γ=90 °), space group P42/ mbc, no dephasign peak, has crystallinity.
By such scheme, nanometer sheet size uniformity rule, a diameter of 0.8-1 μm of nanometer sheet, thickness 20-
40nm, there are the stacking on three-dimensional between nanometer sheet, to reduce the reunion of nanometer sheet, while there are gap between nanometer sheet
In favor of effectively contacting between nanometer sheet and electrolyte.
δ-the VOPO4The preparation method of ultrathin nanometer piece, includes following steps:
1) vanadic anhydride and oxalic acid are added in distilled water, are mixed, obtain VOC2O4Blue solution;
2) it is 1 to measure with vanadic anhydride molar ratio:1 phosphorus source solution, phosphorus source is added dropwise to obtained by step 1) dropwise
VOC2O4In blue solution, stir evenly;
3) precursor solution obtained by step 2) is dried, obtains taupe precursor powder;
4) by precursor powder pre-burning in air atmosphere, forged in air atmosphere again after pre-burning product is somewhat ground
Burn, finally obtain δ-VOPO4Ultrathin nanometer piece.
By such scheme, the molar ratio of vanadic anhydride and oxalic acid described in step 1) is 1:12-1:20, whipping temp is
70-90℃。
By such scheme, the phosphorus source described in step 2) is H3PO4Or NH4H2PO4。
By such scheme, the drying temperature described in step 3) is 120-160 DEG C.
By such scheme, the calcined temperature described in step 4) is 280-350 DEG C, when burn-in time is 3-6 small, calcining heat
For 450-550 DEG C, when calcination time is 8-12 small.
δ-the VOPO4Application of the ultrathin nanometer piece as anode active material of lithium ion battery.
The beneficial effects of the invention are as follows:The present invention mainly passes through simple and practicable sol-gal process combination solid sintering technology
It is prepared for δ-VOPO4Nanometer sheet positive electrode, when it is as anode active material of lithium ion battery, shows power height, circulation
The characteristics of stability is good;Secondly, present invention process is simple, and it is molten to can obtain presoma by simple and practicable sol-gal process
Liquid, solution is dried and air atmosphere under solid-phase sintering can obtain δ-VOPO4Nanometer sheet positive electrode.This method is feasible
Property it is strong, the characteristics of being easy to amplificationization, meet Green Chemistry, beneficial to the marketization promote.
Brief description of the drawings
Fig. 1 is the δ-VOPO of the embodiment of the present invention 14The XRD diagram of ultrathin nanometer piece positive electrode;
Fig. 2 is the δ-VOPO of the embodiment of the present invention 14The SEM figures of ultrathin nanometer piece positive electrode material precursor powder;
Fig. 3 is the δ-VOPO of the embodiment of the present invention 14Gained sample after ultrathin nanometer piece positive electrode material precursor powder pre-burning
SEM figure;
Fig. 4 is the δ-VOPO of the embodiment of the present invention 14The SEM figures of ultrathin nanometer piece positive electrode;
Fig. 5 is the δ-VOPO of the embodiment of the present invention 14The cycle performance of battery figure of ultrathin nanometer piece positive electrode.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Embodiment 1:
δ-VOPO4The preparation method of nanometer sheet positive electrode, it includes the following steps:
1) by 0.637g vanadic anhydrides (V2O5) and 5.046g oxalic acid (C2H2O4) it is added to (V in 30mL distilled water2O5With
The molar ratio 1 of oxalic acid:16), it is mixed 10 minutes at 80 DEG C, obtains VOC2O4Blue solution;
2) it is 1 to measure with vanadium source molar ratio:1 85% phosphoric acid (H3PO4) solution (0.477mL), phosphoric acid is added dropwise to dropwise
In blue solution obtained by step 1), stir evenly;
3) precursor solution obtained by step 2) is dried in drying box, drying temperature is 140 DEG C, obtains taupe presoma
Powder;
4) when by precursor powder, pre-burning 4 is small under 300 DEG C of air atmospheres, again 500 after pre-burning product is somewhat ground
When calcining 10 is small under DEG C air atmosphere, green δ-VOPO are finally obtained4Nanometer sheet positive electrode.
With the product δ-VOPO of the present invention4Exemplified by nanometer sheet positive electrode, its structure is determined by X-ray diffractometer.Such as Fig. 1
It is shown, δ-VOPO4Nanometer sheet positive electrode thing phase and the δ-VOPO that card number is 00-047-09514Standard sample fits like a gloveSample is orthohormbic structure, space group P42/
Mbc, no dephasign peak.The peak of sample is more sharp, illustrates that obtained sample has relatively good crystallinity.
Fig. 2 is the SEM image of gained powder after presoma drying, and as shown in figure, gained sample is solid slug after drying
Shape particle, size is up to tens μm, sample surfaces unusual light, and size is irregular.Fig. 3 is precursor powder in 300 DEG C of air
Splitting takes place in the SEM image of gained sample, the sample block after pre-burning when pre-burning 4 is small under atmosphere, and part-solid block is opened
Beginning is converted to laminated structure, while material surface becomes coarse, this is probably absorption water and part the interlayer crystallization due to material
Water occurs caused by being desorbed.We (scheme obtained precursor powder when reheating processing 10 is small under 500 DEG C of air atmospheres
4), find tens micron-sized block structures be transformed substantially into rule laminated structure, a diameter of 0.8-1 μm of nanometer sheet,
Thickness is only 20-40nm at the same time.Nanometer sheet shows extraordinary dispersiveness, and the accumulation of three-dimensional effectively reduces nanometer sheet
The reunion of material, while there is obviously gap between nanometer sheet, be conducive to effectively contacting between material and electrolyte.
δ-VOPO prepared by the present invention4Nanometer sheet positive electrode is as anode active material of lithium ion battery, lithium-ion electric
Remaining step of the preparation method in pond is identical with common preparation method.The preparation method of positive plate is as follows, using δ-VOPO4Nanometer
Piece positive electrode as active material, acetylene black as conductive agent, polytetrafluoroethylene (PTFE) as binding agent, active material, acetylene black,
The mass ratio of polytetrafluoroethylene (PTFE) is 70:20:10;After they are sufficiently mixed in proportion, a small amount of isopropanol is added, grinding is uniform,
The electrode slice of about 0.5mm thickness is pressed on twin rollers;The positive plate pressed be placed in 80 DEG C oven drying 24 it is small when standby use.With 1M
LiPF6It is dissolved in vinyl carbonate (EC) and dimethyl carbonate (DMC) and is used as electrolyte, lithium piece is anode,
Celgard2325 is membrane, and CR2015 types stainless steel is assembled into fastening lithium ionic cell for battery case.
With the δ-VOPO obtained by the present embodiment4Exemplified by nanometer sheet positive electrode, as shown in figure 5, under 0.5C current densities,
δ-VOPO4The first discharge specific capacity of nanometer sheet positive electrode can reach 174mAh/g, still can reach after circulating 160 times
138mAh/g.Under 1C current densities, the first discharge specific capacity of material still can reach 173mAh/g, and under 0.5C current densities
Discharge capacity it is essentially identical, and circulate 350 times after still can reach 134mAh/g.Under 2C current densities, material is put first
Electric specific capacity is 161mAh/g, and 116mAh/g is still can reach after circulating 500 times.Under 5C current densities, the electric discharge first of material
Specific capacity is 63mAh/g, and with the increase of cycle-index, it is 90mAh/g that the discharge capacity of material increases after circulating 10 times, and
93mAh/g is still can reach after circulating 400 times, shows that material has very excellent high rate performance and cyclical stability.Above-mentioned property
It can be shown that, δ-VOPO4Nanometer sheet positive electrode has very excellent chemical property, be a kind of potential lithium ion battery just
Pole material.
Embodiment 2:
1) by 0.637g vanadic anhydrides (V2O5) and 3.782g oxalic acid (C2H2O4) it is added to (V in 30mL distilled water2O5With
The molar ratio 1 of oxalic acid:12), it is mixed 10 minutes at 70 DEG C, obtains VOC2O4Blue solution;
2) it is 1 to measure with vanadium source molar ratio:1 85% phosphoric acid (H3PO4) solution (0.477mL), phosphoric acid is added dropwise to dropwise
In blue solution obtained by step 1), stir evenly;
3) precursor solution obtained by step 2) is dried in drying box, drying temperature is 120 DEG C, obtains taupe forerunner
Body powder;
4) when by precursor powder, pre-burning 3 is small under 280 DEG C of air atmospheres, again 450 after pre-burning product is somewhat ground
When calcining 8 is small under DEG C air atmosphere, green δ-VOPO are finally obtained4Nanometer sheet positive electrode.
With the δ-VOPO obtained by the present embodiment4Exemplified by nanometer sheet positive electrode, under 1C current densities, δ-VOPO4Nanometer sheet
The first discharge specific capacity of positive electrode can reach 165mAh/g, and specific discharge capacity is 125mAh/g after 350 circulations, capacity
Conservation rate is 75%.
Embodiment 3:
1) by 0.637g vanadic anhydrides (V2O5) and 6.303g oxalic acid (C2H2O4) it is added to (V in 30mL distilled water2O5With
The molar ratio 1 of oxalic acid:20), it is mixed 10 minutes at 90 DEG C, obtains VOC2O4Blue solution;
2) it is 1 to measure with vanadium source molar ratio:1 ammonium dihydrogen phosphate (NH4H2PO4) solution (0.8057g NH4H2PO4It is dissolved in
In 10mL distilled water), by NH4H2PO4Solution is added dropwise in the blue solution obtained by step 1) dropwise, is stirred evenly;
3) precursor solution obtained by step 2) is dried in drying box, drying temperature is 160 DEG C, obtains taupe forerunner
Body powder;
4) when by precursor powder, pre-burning 6 is small under 350 DEG C of air atmospheres, again 500 after pre-burning product is somewhat ground
When calcining 12 is small under DEG C air atmosphere, green δ-VOPO are finally obtained4Nanometer sheet positive electrode.
With the δ-VOPO obtained by the present embodiment4Exemplified by nanometer sheet positive electrode, under 1C current densities, δ-VOPO4Nanometer sheet
The first discharge specific capacity of positive electrode can reach 170mAh/g, and specific discharge capacity is 130mAh/g after 350 circulations, capacity
Conservation rate is 76%.
Embodiment 4:
1) by 0.637g vanadic anhydrides (V2O5) and 4.412g oxalic acid (C2H2O4) it is added to (V in 30mL distilled water2O5With
The molar ratio 1 of oxalic acid:14), it is mixed 10 minutes at 80 DEG C, obtains VOC2O4Blue solution;
2) it is 1 to measure with vanadium source molar ratio:1 85% phosphoric acid (H3PO4) solution (0.477mL), phosphoric acid is added dropwise to dropwise
In blue solution obtained by step 1), stir evenly;
3) precursor solution obtained by step 2) is dried in drying box, drying temperature is 150 DEG C, obtains taupe forerunner
Body powder;
4) when by precursor powder, pre-burning 5 is small under 320 DEG C of air atmospheres, again 550 after pre-burning product is somewhat ground
When calcining 11 is small under DEG C air atmosphere, green δ-VOPO are finally obtained4Nanometer sheet positive electrode.
With the δ-VOPO obtained by the present embodiment4Exemplified by nanometer sheet positive electrode, under 1C current densities, δ-VOPO4Nanometer sheet
The first discharge specific capacity of positive electrode can reach 160mAh/g, and specific discharge capacity is 124mAh/g after 350 circulations, capacity
Conservation rate is 77%.
Embodiment 5:
1) by 0.637g vanadic anhydrides (V2O5) and 5.673g oxalic acid (C2H2O4) it is added to (V in 30mL distilled water2O5With
The molar ratio 1 of oxalic acid:18), it is mixed 10 minutes at 70 DEG C, obtains VOC2O4Blue solution;
2) it is 1 to measure with vanadium source molar ratio:1 ammonium dihydrogen phosphate (NH4H2PO4) solution (0.8057g NH4H2PO4It is dissolved in
In 10mL distilled water), by NH4H2PO4Solution is added dropwise in the blue solution obtained by step 1) dropwise, is stirred evenly;
3) precursor solution obtained by step 2) is dried in drying box, drying temperature is 130 DEG C, obtains taupe forerunner
Body powder;
4) when by precursor powder, pre-burning 3 is small under 320 DEG C of air atmospheres, again 520 after pre-burning product is somewhat ground
When calcining 10 is small under DEG C air atmosphere, green δ-VOPO are finally obtained4Nanometer sheet positive electrode.
With the δ-VOPO obtained by the present embodiment4Exemplified by nanometer sheet positive electrode, under 1C current densities, δ-VOPO4Nanometer sheet
The first discharge specific capacity of positive electrode can reach 163mAh/g, and specific discharge capacity is 127mAh/g after 350 circulations, capacity
Conservation rate is 78%.
Embodiment 6:
1) by 0.637g vanadic anhydrides (V2O5) and 5.046g oxalic acid (C2H2O4) it is added to (V in 30mL distilled water2O5With
The molar ratio 1 of oxalic acid:16), it is mixed 10 minutes at 80 DEG C, obtains VOC2O4Blue solution;
2) it is 1 to measure with vanadium source molar ratio:1 85% phosphoric acid (H3PO4) solution (0.477mL), phosphoric acid is added dropwise to dropwise
In blue solution obtained by step 1), stir evenly;
3) precursor solution obtained by step 2) is dried in drying box, drying temperature is 140 DEG C, obtains taupe forerunner
Body powder;
4) when by precursor powder, pre-burning 4 is small under 310 DEG C of air atmospheres, again 500 after pre-burning product is somewhat ground
When calcining 12 is small under DEG C air atmosphere, green δ-VOPO are finally obtained4Nanometer sheet positive electrode.
With the δ-VOPO obtained by the present embodiment4Exemplified by nanometer sheet positive electrode, under 1C current densities, δ-VOPO4Nanometer sheet
The first discharge specific capacity of positive electrode can reach 168mAh/g, and specific discharge capacity is 125mAh/g after 350 circulations, capacity
Conservation rate is 74%.
Claims (8)
1.δ-VOPO4Ultrathin nanometer piece, it is orthohormbic structure, thing phase and the δ-VOPO that card number is 00-047-09514Standard sample
Product fit like a glove (α=90 °, β=90 °, γ=90 °), space group P42/ mbc,
Without dephasign peak, there is crystallinity.
2. δ-VOPO according to claim 14Ultrathin nanometer piece, it is characterised in that the nanometer sheet size uniformity rule,
A diameter of 0.8-1 μm of nanometer sheet, thickness 20-40nm, there are the stacking on three-dimensional between nanometer sheet, to reduce nanometer
The reunion of piece, at the same between nanometer sheet there are gap in favor of between nanometer sheet and electrolyte effectively contacting.
3. δ-the VOPO described in claim 14The preparation method of ultrathin nanometer piece, includes following steps:
1) vanadic anhydride and oxalic acid are added in distilled water, are mixed, obtain VOC2O4Blue solution;
2) it is 1 to measure with vanadic anhydride molar ratio:Phosphorus source, is added dropwise to the VOC obtained by step 1) by 1 phosphorus source solution dropwise2O4
In blue solution, stir evenly;
3) precursor solution obtained by step 2) is dried, obtains taupe precursor powder;
4) by precursor powder pre-burning in air atmosphere, calcined in air atmosphere again after pre-burning product is somewhat ground, most
δ-VOPO are obtained eventually4Ultrathin nanometer piece.
4. δ-VOPO according to claim 34The preparation method of ultrathin nanometer piece, it is characterised in that five described in step 1)
The molar ratio of V 2 O and oxalic acid is 1:12-1:20, whipping temp is 70-90 DEG C.
5. δ-VOPO according to claim 34The preparation method of ultrathin nanometer piece, it is characterised in that the phosphorus described in step 2)
Source is H3PO4Or NH4H2PO4。
6. δ-VOPO according to claim 34The preparation method of ultrathin nanometer piece, it is characterised in that the baking described in step 3)
Dry temperature is 120-160 DEG C.
7. δ-VOPO according to claim 34The preparation method of ultrathin nanometer piece, it is characterised in that pre- described in step 4)
It is 280-350 DEG C to burn temperature, and when burn-in time is 3-6 small, calcining heat is 450-550 DEG C, when calcination time is 8-12 small.
8. δ-the VOPO described in claim 14Application of the ultrathin nanometer piece as anode active material of lithium ion battery.
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CN112701283A (en) * | 2020-12-29 | 2021-04-23 | 东北师范大学 | Positive electrode material and preparation method and application thereof |
CN113299900A (en) * | 2021-05-11 | 2021-08-24 | 南京工业大学 | Ultrathin transition amorphous layer material and preparation method and application thereof |
CN113457700A (en) * | 2021-06-24 | 2021-10-01 | 浙江大学 | Vanadium-phosphorus-oxygen catalyst for aldol condensation and preparation method and application thereof |
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CN113299900B (en) * | 2021-05-11 | 2022-04-12 | 南京工业大学 | Ultrathin transition amorphous layer material and preparation method and application thereof |
CN113457700A (en) * | 2021-06-24 | 2021-10-01 | 浙江大学 | Vanadium-phosphorus-oxygen catalyst for aldol condensation and preparation method and application thereof |
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