CN107611420A - A kind of lithium battery nano-electrode material LiNaV2O6And preparation method thereof - Google Patents
A kind of lithium battery nano-electrode material LiNaV2O6And preparation method thereof Download PDFInfo
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- CN107611420A CN107611420A CN201710756556.7A CN201710756556A CN107611420A CN 107611420 A CN107611420 A CN 107611420A CN 201710756556 A CN201710756556 A CN 201710756556A CN 107611420 A CN107611420 A CN 107611420A
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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
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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 discloses a kind of lithium battery nano-electrode material LiNaV2O6And preparation method thereof, the preparation method comprises the steps of：By elemental mole ratios in molecular formula, lithium source, sodium source, vanadium source are added in the aqueous solution of acrylic acid, and add acid for adjusting pH value and form stable, aqueous solution, gel dry powder is formed by thermal polymerization, gained dry powder is ground and is heat-treated can obtain nano-powder material LiNaV2O6.The present invention realizes being sufficiently mixed for different material using wet chemistry method, by the stable V element of acrylic acid complex reaction, forms xerogel using acrylic acid thermal polymerization and suppresses granular grows in heat treatment process, simply and effectively prepare nano material；By the Na that ionic radius is larger+It is introduced into layer structure, realizes LiNaV2O6The lifting of material lithium ion transmission rate and structural stability；When the material is as anode material of lithium battery, gram volume is high, and cycle performance and high rate performance are preferable；The advantages that being provided simultaneously with simple preparation technology, short preparation period, efficiency high.
Description
Technical field
The present invention relates to lithium battery material field, specifically a kind of lithium battery nano-electrode material LiNaV2O6And its prepare
Method.
Background technology
With the continuous growth of energy demand, explore the new energy energy storage device for possessing premium properties and energy storage material into
One of focus for current development in science and technology.Wherein, lithium battery is because it is with higher energy density, longer cycle life, nothing
The advantages such as memory effect, security are higher and the feature of environmental protection is good, obtain extensive concern and fast development.In the numerous of lithium battery
During key is formed, positive electrode is to influence battery energy density, power density, cycle life and an important factor for security performance,
It is the part of lithium battery most critical.Wherein, possess the positive electrode of layer structure because of its good structural stability and compared with
High lithium ion transport speed and as conventional positive electrode, such as widely used stratiform cobalt acid lithium and ternary material.But
In such material, generally existing gram volume is relatively low to cause that energy density is high, scarcity of resources causes the shortcomings of with high costs.
Compared with currently used layered cathode material, layer structure vanadium system positive electrode such as V2O5、LiVO3And LiV3O8
The advantages that vanadium resource is abundant, synthesis technique is simple, cost is low, gram volume is high, energy density is high is also equipped with, is ideal lithium
Cell positive material.But as the increase of Lithium-ion embeding amount, the layer structure of such material can produce in charge and discharge process
Disordering and irreversible transition, the reduction and cycle performance decay of material gram volume are caused, limits the application of such material.
The content of the invention
It is an object of the invention to provide a kind of lithium battery nano-electrode material LiNaV2O6And preparation method thereof, the material
Structural stability and lithium ion conductivity it is higher, preparation technology is simple, short preparation period, efficiency high.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of lithium battery nano-electrode material LiNaV2O6Preparation method, comprise the following steps：
(1) LiNaV is pressed2O6Elemental mole ratios in molecular formula, lithium source, sodium source, vanadium source are added in the aqueous solution of acrylic acid,
And add acid for adjusting pH value and form stable, aqueous solution；
(2) aqueous solution obtained in step (1) is warming up to T1 and be incubated, the aqueous solution is formed gel and be dried to fluffy
Dry powder；
(3) the dry powder milled processed that will be obtained in step (2), be warming up to temperature T2 carry out be heat-treated reaction obtain nano powder
Body material LiNaV2O6。
Preferably, one or more of the lithium source in the step (1) in lithium acetate, lithium nitrate, lithium hydroxide.
Preferably, the sodium source in the step (1) be selected from sodium acetate, sodium nitrate, sodium carbonate, sodium hydroxide, sodium metavanadate,
One or more in sodium vanadate.
Preferably, the vanadium source in the step (1) is in ammonium metavanadate, vanadic anhydride, sodium metavanadate, sodium vanadate
It is one or more.
Preferably, the pH value regulation acid in the step (1) is in nitric acid, hydrochloric acid, oxalic acid, citric acid, tartaric acid
One or more.
Preferably, vanadium ion molar concentration is not higher than 0.3 mol/L in the aqueous solution in the step (1), vanadium ion with
Acrylic acid molar ratio is not higher than 1, and pH value of water solution is not higher than 2.5.
Preferably, holding temperature T1 is 80-200 DEG C in the step (2), soaking time 1.5-48h.
Preferably, sintered heat insulating temperature T2 is 300-600 DEG C in the step (3), heat treatment time 6-24h.
It is another object of the present invention to provide the lithium battery nano-electrode material that a kind of above method is prepared
LiNaV2O6。
Beneficial effects of the present invention：The present invention passes through the larger Na of ionic radius+The less Li of substitution ion radius+, can expand
The lithium ion transport passage in layer structure is opened, is advantageous to be lifted the lithium ion transport speed of material；Na elements are with Li elements
Same main group adjacent element, LiVO3With NaVO3Belong to monoclinic system together, space group is all C2/c, can form stable solid solution, knot
Structure stability is lifted；By the stable V element of acrylic acid complex reaction, xerogel is formed using acrylic acid thermal polymerization, is suppressed at heat
Nano particle is grown up during reason, can obtain nanometer sized materials.Nanometer LiNaV of the present invention2O6Materials application is in lithium
During cell positive material, the advantages of keeping high gram volume, and lithium ion transport speed is high, can be lifted material cycle performance and
High rate performance；And preparation technology is simple, short preparation period, efficiency high.
Embodiment
The present invention is described in further detail with reference to specific embodiment.
Comparative example：Example 1 in molar ratio:1 weighs raw material lithium acetate and vanadic anhydride, after dry mixed is uniform, under air
450 DEG C are warming up to, insulation 12h can obtain LiVO3Material.
Embodiment 1：Example 1 in molar ratio:1:2:4 are added to the water lithium nitrate, sodium nitrate, ammonium metavanadate and acrylic acid,
It is added dropwise 1:3 nitric acid form the aqueous solution, and pH value of water solution 1.5, vanadium ion molar concentration is 0.15 mol/L.By this solution liter
Temperature obtains fluffy dry powder to 150 DEG C of insulation 15h, is heat-treated 10h at 350 DEG C after ground and mixed, you can obtain nanometer
LiNaV2O6Material.
Embodiment 2：Example 1 in molar ratio:1:1:Lithium acetate, sodium acetate, vanadic anhydride and acrylic acid are added to water by 3
In, it is added dropwise 1:2 hydrochloric acid form the aqueous solution, and pH value of water solution 1, vanadium ion molar concentration is 0.1 mol/L.By this solution liter
Temperature obtains fluffy dry powder to 180 DEG C of insulation 6h, is heat-treated 8h at 450 DEG C after ground and mixed, you can obtain a nanometer LiNaV2O6
Material.
Embodiment 3：Example 1 in molar ratio:1:0.5:2.5 add lithium acetate, sodium metavanadate, vanadic anhydride and acrylic acid
Into water, add oxalic acid and form the aqueous solution, pH value of water solution 2, vanadium ion molar concentration is 0.15 mol/L.By this solution
It is warming up to 100 DEG C of insulation 15h and obtains fluffy dry powder, is heat-treated 24h at 300 DEG C after ground and mixed, you can obtain nanometer
LiNaV2O6Material.
Embodiment 4：Example 3 in molar ratio:1:5:Lithium hydroxide, sodium vanadate, ammonium metavanadate and acrylic acid are added to water by 6
In, add 1:1 nitric acid forms the aqueous solution, and pH value of water solution 1.5, vanadium ion molar concentration is 0.3 mol/L.By this solution
It is warming up to 80 DEG C of insulation 48h and obtains fluffy dry powder, is heat-treated 12h at 500 DEG C after ground and mixed, you can obtain nanometer
LiNaV2O6Material.
Embodiment 5：Example 1 in molar ratio:1:2:Lithium acetate, sodium acetate, ammonium metavanadate and acrylic acid are added to water by 3.5
In, add tartaric acid and form the aqueous solution, pH value of water solution 2.5, vanadium ion molar concentration is 0.05 mol/L.By this solution
It is warming up to 200 DEG C of insulation 1.5h and obtains fluffy dry powder, is heat-treated 6h at 600 DEG C after ground and mixed, you can obtain nanometer
LiNaV2O6Material.
The particle diameter of material is characterized by electronic scanner microscope prepared by comparative example and embodiment, lithium ion mobility speed
Rate is characterized by constant current Intermittent Titration method (GITT), and chemical property is characterized by the test of 2016 button cells.
Button cell makes and method of testing is：Pole piece proportioning is active material：Conductive agent acetylene black：Binding agent Kynoar PVDF
=8:1:1, lithium piece is to electrode, and 2016 button half-cells are prepared in the glove box full of argon gas.Half-cell discharge and recharge section is
After 1.5-4.0V, 0.1C charge and discharge cycles 3 times, then carry out the cycle performance test under 1C.
Following table is that the physical and chemical performance of material in each embodiment characterizes contrast.As can be seen that LiVO prepared by comparative example3Material
Particle diameter is micron level, and average grain diameter is maximum, and aids in the LiNaV of preparation in embodiment by acrylic acid2O6Material granule is averaged
Particle diameter is both less than 500nm.The lithium ion mobility speed of various materials is tested by constant current Intermittent Titration method (GITT), can be seen
Go out, nanoscale LiNaV2O6The lithium ion mobility speed of material is far above micron order LiVO3Material.Electrochemical results also table
It is bright, nanoscale LiNaV2O60.1C and 1C specific discharge capacities, the cycle performance of material are better than micron order LiVO3Material.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.Person skilled in the art obviously can easily make various modifications to case study on implementation, and described herein one
As principle be applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation case here
Example, for those skilled in the art according to the announcement of the present invention, not departing from improvement that scope made and modification all should be
Within protection scope of the present invention.
Claims (9)
- A kind of 1. lithium battery nano-electrode material LiNaV2O6Preparation method, it is characterised in that comprise the following steps：（1）By LiNaV2O6Elemental mole ratios in molecular formula, lithium source, sodium source, vanadium source are added in the aqueous solution of acrylic acid, and added Enter acid for adjusting pH value and form stable, aqueous solution；（2）By step（1）In the obtained aqueous solution be warming up to T1 and be incubated, the aqueous solution is formed gel and be dried to fluffy dry Powder；（3）By step（2）In obtained dry powder milled processed, be warming up to temperature T2 and carry out being heat-treated reaction and obtain nano-powder material Expect LiNaV2O6。
- 2. lithium battery nano-electrode material LiNaV according to claim 12O6Preparation method, it is characterised in that it is described Step（1）In one or more of the lithium source in lithium acetate, lithium nitrate, lithium hydroxide.
- 3. lithium battery nano-electrode material LiNaV according to claim 12O6Preparation method, it is characterised in that it is described Step（1）In one kind or more in sodium acetate, sodium nitrate, sodium carbonate, sodium hydroxide, sodium metavanadate, sodium vanadate of sodium source Kind.
- 4. lithium battery nano-electrode material LiNaV according to claim 12O6Preparation method, it is characterised in that it is described Step（1）In one or more of the vanadium source in ammonium metavanadate, vanadic anhydride, sodium metavanadate, sodium vanadate.
- 5. lithium battery nano-electrode material LiNaV according to claim 12O6Preparation method, it is characterised in that it is described Step（1）In one or more of the pH value regulation acid in nitric acid, hydrochloric acid, oxalic acid, citric acid, tartaric acid.
- 6. lithium battery nano-electrode material LiNaV according to claim 12O6Preparation method, it is characterised in that it is described Step（1）In the aqueous solution in vanadium ion molar concentration be not higher than 0.3 mol/L, vanadium ion is not high with acrylic acid molar ratio In 1, pH value of water solution is not higher than 2.5.
- 7. lithium battery nano-electrode material LiNaV according to claim 12O6Preparation method, it is characterised in that it is described Step（2）Middle holding temperature T1 is 80-200 DEG C, soaking time 1.5-48h.
- 8. lithium battery nano-electrode material LiNaV according to claim 12O6Preparation method, it is characterised in that it is described Step（3）Middle sintered heat insulating temperature T2 is 300-600 DEG C, heat treatment time 6-24h.
- 9. the lithium battery nano-electrode material LiNaV that claim 1 method is prepared2O6。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111952580A (en) * | 2020-08-28 | 2020-11-17 | 天津工业大学 | Preparation method of vanadium-based nano material for anode of water-based zinc ion battery |
| WO2024000101A1 (en) * | 2022-06-27 | 2024-01-04 | 宁德时代新能源科技股份有限公司 | Secondary battery, battery module, battery pack, and electrical device |
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| CN1225195A (en) * | 1996-07-11 | 1999-08-04 | 贝尔通讯研究股份有限公司 | A method for preparing mixed amorphous vanadium oxides and their use as electrodes in rechargeable lithium cells |
| CN1624211A (en) * | 2004-10-26 | 2005-06-08 | 武汉理工大学 | Large scale in situ preparation method of ternary NaV6O15 single crystal nanometer needle |
| CN105720254A (en) * | 2016-03-02 | 2016-06-29 | 合肥国轩高科动力能源有限公司 | Preparation method for carbon-coated lithium vanadate used as negative electrode material of lithium ion battery |
| CN106192006A (en) * | 2015-05-08 | 2016-12-07 | 中国科学院新疆理化技术研究所 | Compound lithium vanadate sodium optical crystal and its production and use |
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2017
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1225195A (en) * | 1996-07-11 | 1999-08-04 | 贝尔通讯研究股份有限公司 | A method for preparing mixed amorphous vanadium oxides and their use as electrodes in rechargeable lithium cells |
| CN1624211A (en) * | 2004-10-26 | 2005-06-08 | 武汉理工大学 | Large scale in situ preparation method of ternary NaV6O15 single crystal nanometer needle |
| CN106192006A (en) * | 2015-05-08 | 2016-12-07 | 中国科学院新疆理化技术研究所 | Compound lithium vanadate sodium optical crystal and its production and use |
| CN105720254A (en) * | 2016-03-02 | 2016-06-29 | 合肥国轩高科动力能源有限公司 | Preparation method for carbon-coated lithium vanadate used as negative electrode material of lithium ion battery |
Cited By (3)
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|---|---|---|---|---|
| CN111952580A (en) * | 2020-08-28 | 2020-11-17 | 天津工业大学 | Preparation method of vanadium-based nano material for anode of water-based zinc ion battery |
| CN111952580B (en) * | 2020-08-28 | 2022-04-01 | 天津工业大学 | Preparation method of vanadium-based nano material for anode of water-based zinc ion battery |
| WO2024000101A1 (en) * | 2022-06-27 | 2024-01-04 | 宁德时代新能源科技股份有限公司 | Secondary battery, battery module, battery pack, and electrical device |
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