CN106745251B - A kind of preparation method and application of nanometer vanadic anhydride positive electrode suitable for industrialized production - Google Patents
A kind of preparation method and application of nanometer vanadic anhydride positive electrode suitable for industrialized production Download PDFInfo
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- CN106745251B CN106745251B CN201611095638.3A CN201611095638A CN106745251B CN 106745251 B CN106745251 B CN 106745251B CN 201611095638 A CN201611095638 A CN 201611095638A CN 106745251 B CN106745251 B CN 106745251B
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 43
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 13
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 239000006183 anode active material Substances 0.000 claims abstract description 5
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 5
- 238000001694 spray drying Methods 0.000 claims abstract description 5
- 239000007921 spray Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- RLXDCJUIXHSXQD-UHFFFAOYSA-N oxalic acid;hydrate Chemical class O.OC(=O)C(O)=O.OC(=O)C(O)=O RLXDCJUIXHSXQD-UHFFFAOYSA-N 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 244000283207 Indigofera tinctoria Species 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 206010068052 Mosaicism Diseases 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 description 1
- 210000003765 sex chromosome Anatomy 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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 method and application of the nanometer vanadic anhydride positive electrode suitable for industrialized production, includes the following steps：Vanadium source and oxalic acid are add to deionized water, blue solution is formed；Additive, ethylene glycol are added separately in blue solution, blue precursor solution is obtained；Blue precursor solution is spray-dried, blue presoma powder is obtained；Blue presoma powder is subjected to aerobic sintering, is sieved to get product.The present invention uses liquid phase-spray drying technology, and product particle is nanoscale, and is evenly distributed, and has excellent chemical property, and raw material sources are wide, preparation process is simple, at low cost, is easy to industrialization, can be used as anode active material of lithium ion battery.
Description
Technical field
The present invention relates to nanometer material and electrochemical technology fields, and in particular to a kind of nanometer five suitable for industrialized production
V 2 O (V2O5) positive electrode preparation method.
Background technology
Lithium ion battery has many advantages, such as high-energy-density, long lifespan, green low-carbon, in electric vehicle, consumer electronics city
Field is equal to be gradually used widely, but due to poor high rate performance and power density, limits it and is advised greatly in electric vehicle etc.
Application in mould energy stores.?《Energy saving and new-energy automobile national planning》In point out, end the year two thousand twenty power battery energy
Density will reach 300Wh/Kg, while in national " 13 " new-energy automobile emphasis special project, also explicitly pointing out will reach
This target of 300Wh/Kg.However current LiFePO 4 material, ternary material all temporarily cannot be satisfied this demand, need to send out
Novel anode material is opened up to meet this target.In positive electrode, layer structure V2O5At most can with 3 lithium ions of deintercalation, and
It is resourceful, the high advantage of theoretical capacity and be widely recognized.But it is still there is two large problems, poor high rate performance and
Stable circulation sex chromosome mosaicism.
Nano material has high specific surface area and preferably activity, when as lithium ion battery electrode material and is electrolysed
Liquid contact area is big, lithium ion deintercalation is apart from short, the electro-chemical activity of material can be effectively improved, as high multiplying power lithium ion battery
There is significant advantage when electrode material.However, the excellent V of current processability2O5Positive electrode mostly uses greatly hydro-thermal method, sinks
Shallow lake method, the methods of sol method there is low production efficiency, process complexity, be unfavorable for the shortcomings of industrialization, limit five oxidations
Application of two vanadium in lithium battery.
Invention content
The object of the present invention is to provide a kind of preparation sides of the nanometer vanadic anhydride positive electrode suitable for industrialized production
Method, using liquid phase-spray drying technology, product particle is nanoscale, and is evenly distributed, and has excellent chemical property, and former
Expect that source is wide, preparation process is simple, at low cost, is easy to industrialization, can be used as anode active material of lithium ion battery.
To achieve the goals above, the technical solution adopted by the present invention is as follows：
A kind of preparation method of nanometer vanadic anhydride positive electrode suitable for industrialized production, includes the following steps：
1) vanadium source and oxalic acid are add to deionized water, form blue solution；
2) additive, ethylene glycol (EG) are added separately in blue solution, obtain blue precursor solution；
3) blue precursor solution is spray-dried, obtains blue presoma powder；
4) blue presoma powder is subjected to aerobic sintering, sieved to get product.
According to above scheme, the vanadium source is V2O5, ammonium metavanadate (NH4VO3) or both mixture.
According to above scheme, the molar ratio of the oxalic acid and vanadium in the vanadium source is 1~9.
According to above scheme, the additive is polyvinyl alcohol (PVA), glucose, polyvinylpyrrolidone (PVP), sugarcane
Any one in sugar, soluble starch, polyethylene glycol (PEG), citric acid or more than one mixture.
According to above scheme, the ethylene glycol is converted into V with the vanadium source2O5Mass ratio afterwards is 1/16~1/2, described
The density of ethylene glycol is 1.1155g/mL.
According to above scheme, the spray drying is using Pressuresprayingdrier, drying machine with centrifugal spray or air-flowing type spray
Mist drying machine.
According to above scheme, the temperature of the aerobic sintering is 350 DEG C -550 DEG C, time 1-8h.
According to above scheme, the nanometer vanadic anhydride positive electrode is as anode active material of lithium ion battery.
The present invention is prepared for a nanometer V using the liquid phase-drying process with atomizing for being easy to industrialization2O5Positive electrode, mesoxalic acid
Preparing precursor solution with the generation chemical reaction of vanadium source, (solution refers to the particle diameter of dispersate<The disperse system of 1nm), pass through spray
Mist drying can overlap nano particle together, form the 100-500nm nanometers V being evenly distributed2O5Positive electrode shortens lithium
Ion diffusion path improves effective contact area of electrode material and electrolyte, to obtain long-life, powerful electrification
Learn performance.
The beneficial effects of the invention are as follows：
1) present invention uses liquid phase-drying process with atomizing, simple process and low cost, and raw material sources are wide, product particle ruler
It is very little and to be evenly distributed in 100nm-500nm, have the advantages that discharge capacity is high, power is high, good cycling stability, can be used as lithium
Ion battery positive electrode active materials；
2) feasibility of the invention is strong, the characteristics of being easy to amplify metaplasia production, meet Green Chemistry, is conducive to the marketization and promotes.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention；
Fig. 2 is the XRD diagram of 1 product of the embodiment of the present invention；
Fig. 3 is the SEM figures of 1 product of the embodiment of the present invention；
Fig. 4 is 0.1C (1C=150mAh/g) charging and discharging capacity curve graph of 1 product of the embodiment of the present invention；
Fig. 5 is the cycle performance of battery figure of 1 product of the embodiment of the present invention.
Specific implementation mode
Technical scheme of the present invention is illustrated with embodiment below in conjunction with the accompanying drawings.
Embodiment 1 is shown in Fig. 1 to Fig. 5：
The present invention provides a kind of preparation method of the nanometer vanadic anhydride positive electrode suitable for industrialized production, including such as
Lower step (see attached drawing 1)：
1) by 16.368Kg V2O5, bis- oxalic acid hydrates of 68.1Kg be add to deionized water, formed blue solution；
2) 15Kg PVA and 5L EG (density 1.1155g/mL) are added separately in blue solution, before obtaining blue
Drive liquid solution；
3) blue precursor solution is squeezed into centrifugal spray dryer with pump to be spray-dried, obtains blue presoma
Powder；
4) by blue presoma powder under aerobic conditions 500 DEG C sintering 3h, sieve to get product.
The structure of the present embodiment product is measured by X-ray diffractometer, as a result sees attached drawing 2, X ray diffracting spectrum (XRD) table
Bright, nano-powder structure is V2O5(JCPDS card numbers are 00-041-1426), without other dephasigns.
The SEM figures of the present embodiment product are shown in attached drawing 3, the results showed that, grain diameter size between 100nm-500nm, and
Even particle distribution.
The present embodiment products obtained therefrom nanometer V2O5Particle is as follows as the application of anode active material of lithium ion battery：Anode
The preparation process of piece uses nanometer V2O5Positive electrode is as active material, and acetylene black is as conductive agent, and polytetrafluoroethylene (PTFE) is as viscous
Tie agent, active material, acetylene black, polytetrafluoroethylene (PTFE) mass ratio be 80:10:10；After they are sufficiently mixed in proportion, it is added
A small amount of isopropanol, grinding is uniform, and the electrode slice of about 0.5mm thickness is pressed on twin rollers；The positive plate pressed is placed in 80 DEG C of baking oven
It is spare after 24 hours dry.With the LiPF of 1M6It is dissolved in vinyl carbonate (EC) and dimethyl carbonate (DMC) as electrolysis
Liquid, lithium piece are cathode, and Celgard2325 is diaphragm, and CR2025 type stainless steels are that battery case is assembled into fastening lithium ionic cell.
Remaining step of the preparation method of lithium ion battery is identical as common preparation method.
0.1C (1C=150mAh/g) charging and discharging capacity curve of the present embodiment product is as shown in Fig. 4.V2O5Electrification
Process is extremely complex, when charge and discharge section is 2.5-4V, has 1 lithium ion to carry out deintercalation, can show 2 charge and discharge
Platform.As can be seen from the figure it has 2 platforms that can obviously be observed, and charge and discharge platform pressure difference very little, it is shown that nanometer
V2O5The excellent structural stability of particle.
The cycle performance of battery of the present embodiment product is as shown in Fig. 5, nanometer V2O5Positive electrode is in 2.5-4V (1C=
150mAh/g), its specific capacity can respectively reach and reach 124.7mAh/g in the case of 0.5C, its specific capacity is still after 200 cycles
115.9mAh/g, capacity retention ratio 92.9%, while the efficiency for charge-discharge of material can be reached and be always held at 100% left side
It is right.It should be the result shows that nanometer V2O5Particle has excellent cyclical stability, is high-energy, high power, extended-life lithium ion battery
Potential application material.
Embodiment 2：
The present invention provides a kind of preparation method of the nanometer vanadic anhydride positive electrode suitable for industrialized production, including such as
Lower step：
1) by 21.055Kg NH4VO3, bis- oxalic acid hydrates of 68.1Kg be add to deionized water, formed blue solution；
2) 12Kg PEG-4000 and 2L EG (density 1.1155g/mL) are added separately in blue solution, obtain indigo plant
Color precursor solution；
3) blue precursor solution is squeezed into centrifugal spray dryer with pump to be spray-dried, obtains blue presoma
Powder；
4) by blue presoma powder under aerobic conditions 350 DEG C sintering 8h, sieve to get product.
The present embodiment resulting product nanometer V2O5As the positive electrode active materials of lithium ion, in 2.5-4V (1C=
150mAh/g), its specific capacity can reach 126.7mAh/g in the case of 0.5C, its specific capacity still reaches after 200 cycles
116.7mAh/g, capacity retention ratio 92.1%.
Embodiment 3：
The present invention provides a kind of preparation method of the nanometer vanadic anhydride positive electrode suitable for industrialized production, including such as
Lower step：
1) by 16.368Kg V2O5, bis- oxalic acid hydrates of 136.2Kg be add to deionized water, formed blue solution；
2) 15Kg glucose and 2L EG (density 1.1155g/mL) are added separately in blue solution, obtain blue
Precursor solution；
3) blue precursor solution is squeezed into centrifugal spray dryer with pump to be spray-dried, obtains blue presoma
Powder；
4) by blue presoma powder under aerobic conditions 550 DEG C sintering 8h, sieve to get product.
The present embodiment resulting product nanometer V2O5As the positive electrode active materials of lithium ion, in 2.5-4V (1C=
150mAh/g), its specific capacity can reach 125.7mAh/g in the case of 0.5C, its specific capacity still reaches after 200 cycles
114.2mAh/g, capacity retention ratio 90.8%.
Embodiment 4：
The present invention provides a kind of preparation method of the nanometer vanadic anhydride positive electrode suitable for industrialized production, including such as
Lower step：
1) by 21.055Kg NH4VO3, bis- oxalic acid hydrates of 35Kg be add to deionized water, formed blue solution；
2) 10Kg PVP (K-30) and 6L EG (density 1.1155g/mL) are added separately in blue solution, are obtained
Blue precursor solution；
3) blue precursor solution is squeezed into centrifugal spray dryer with pump to be spray-dried, obtains blue presoma
Powder；
4) by blue presoma powder under aerobic conditions 520 DEG C sintering 2h, sieve to get product.
The present embodiment resulting product nanometer V2O5As the positive electrode active materials of lithium ion, in 2.5-4V (1C=
150mAh/g), its specific capacity can reach 122.1mAh/g in the case of 0.5C, its specific capacity still reaches after 200 cycles
110.9mAh/g, capacity retention ratio 90.8%.
Embodiment 5：
The present invention provides a kind of preparation method of the nanometer vanadic anhydride positive electrode suitable for industrialized production, including such as
Lower step：
1) by 16.368Kg V2O5, bis- oxalic acid hydrates of 204.3Kg be add to deionized water, formed blue solution；
2) 15Kg sucrose and 5L EG (density 1.1155g/mL) are added separately in blue solution, before obtaining blue
Drive liquid solution；
3) blue precursor solution is squeezed into centrifugal spray dryer with pump to be spray-dried, obtains blue presoma
Powder；
4) by blue presoma powder under aerobic conditions 480 DEG C sintering 5h, sieve to get product.
The present embodiment resulting product nanometer V2O5As the positive electrode active materials of lithium ion, in 2.5-4V (1C=
150mAh/g), its specific capacity can reach 128.7mAh/g in the case of 0.5C, its specific capacity still reaches after 200 cycles
113.1mAh/g, capacity retention ratio 87.9%.
Embodiment 6：
The present invention provides a kind of preparation method of the nanometer vanadic anhydride positive electrode suitable for industrialized production, including such as
Lower step：
1) by 16.368Kg V2O5, bis- oxalic acid hydrates of 68.1Kg be add to deionized water, formed blue solution；
2) by 15Kg soluble starches and and 2L EG (density 1.1155g/mL) be added separately in blue solution, obtain
To blue precursor solution；
3) blue precursor solution is squeezed into centrifugal spray dryer with pump to be spray-dried, obtains blue presoma
Powder；
4) by blue presoma powder under aerobic conditions 500 DEG C sintering 8h, sieve to get product.
The present embodiment resulting product nanometer V2O5As the positive electrode active materials of lithium ion, in 2.5-4V (1C=
150mAh/g), its specific capacity can reach 120.3mAh/g in the case of 0.5C, its specific capacity still reaches after 200 cycles
109.5mAh/g, capacity retention ratio 91.0%.
The above embodiments are only used to illustrate and not limit the technical solutions of the present invention, although above-described embodiment to the present invention into
Detailed description is gone, the related technical personnel of this field should understand that：It can modify to the present invention or replace on an equal basis, but
Any modification and part replacement for not departing from spirit and scope of the invention should all be covered in scope of the presently claimed invention.
Claims (4)
1. a kind of preparation method of nanometer vanadic anhydride positive electrode suitable for industrialized production, which is characterized in that including such as
Lower step：
1）Vanadium source and oxalic acid are add to deionized water, blue solution is formed；
2）Additive, ethylene glycol are added separately in blue solution, blue precursor solution is obtained；
3）Blue precursor solution is spray-dried, blue presoma powder is obtained；
4）Blue presoma powder is subjected to aerobic sintering, is sieved to get product；
The molar ratio of the oxalic acid and vanadium in the vanadium source is 1 ~ 9；
The additive is polyvinyl alcohol, glucose, polyvinylpyrrolidone, sucrose, soluble starch, polyethylene glycol, lemon
It is more than any one in acid；
The spray drying uses Pressuresprayingdrier, drying machine with centrifugal spray or air flow type spray drying machine；
The temperature of the aerobic sintering is 350 DEG C -550 DEG C, time 1-8h.
2. the preparation method of the nanometer vanadic anhydride positive electrode according to claim 1 suitable for industrialized production,
It is characterized in that, the vanadium source is V2O5、NH4VO3Or both mixture.
3. the preparation method of the nanometer vanadic anhydride positive electrode according to claim 1 suitable for industrialized production,
It is characterized in that, the ethylene glycol is converted into V with the vanadium source2O5Mass ratio afterwards is 1/16 ~ 1/2, and the density of the ethylene glycol is
1.1155g/mL。
4. the preparation method of the nanometer vanadic anhydride positive electrode according to claim 1 suitable for industrialized production,
It is characterized in that, the nanometer vanadic anhydride positive electrode is as anode active material of lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611095638.3A CN106745251B (en) | 2016-11-30 | 2016-11-30 | A kind of preparation method and application of nanometer vanadic anhydride positive electrode suitable for industrialized production |
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| 钒-基纳米材料或纳米复合材料用作锂电池正极材料的性能研究;潘安强;《中国博士学位论文全文数据库 工程科技II辑》;20111215(第12期);第43页最后一段，第44页第3段 * |
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