CN109305700B - Preparation method of niobium/tantalum cation-containing disordered rock salt structure cathode material - Google Patents
Preparation method of niobium/tantalum cation-containing disordered rock salt structure cathode material Download PDFInfo
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Abstract
The invention discloses a preparation method of a niobium/tantalum cation-containing disordered rock salt structure cathode material, and belongs to the field of new energy materials. The method adopts a stable water-soluble citric acid Nb/Ta precursor, synthesizes the oxide anode material containing the Nb/Ta cation disordered rock salt structure by a wet chemical method, and has the advantages of simple synthesis process, easy reaction control, high production efficiency and no need of special equipment/protection. The invention can improve the phase purity of the oxide, optimize the grain size and the like, and simultaneously improve the electrochemical performance of the oxide anode material.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to a preparation method of a niobium/tantalum cation-containing disordered rock salt structure cathode material.
Background
The lithium ion battery has a series of outstanding advantages of high energy density, light weight, no memory effect, good rate capability, long cycle life and the like, and is recognized as an ideal energy source for the next generation of electric vehicles and hybrid electric vehicles. Since the energy density of lithium ion batteries mainly depends on the energy density of a positive electrode material, development of a positive electrode material having a high energy density has been focused.
The ordered rock salt structure layered positive electrode material is taken as one of the large groups of positive electrode materials and is consistently seen by the scientific community. The ordered structure of the positive electrode material has been considered as an important condition for obtaining high capacity and good cycle performance. At present, in commercial lithium ion batteries, the mainstream positive electrode material is an oxide in an ordered close packing arrangement, such as a ternary positive electrode material-cobalt nickel lithium manganate (LiNi)xCoyMn1-x-yO2For short, NCM, x + y is more than or equal to 0 and less than or equal to 1, x is more than 0 and less than1,0 < y < 1) and spinel-structured lithium ion transition metal oxide LiFePO4And the like. Under the high lithium removal state, the ordered layered structure of the anode material can be gradually changed into an unordered rock salt structure, so that the discharge capacity of the anode material is reduced, the cycle performance is reduced, and the like. Researchers often employ different modification means (e.g., doping, cladding, etc.) to suppress this structural disorder transition.
Previously, the scholars considered that the mixed or disordered arrangement structure of cations was not favorable for the migration of lithium ions. In recent years, the Ceder team of Massachusetts university of technology uses the cation disordered oxide Li1.211Mo0.467Cr0.3O2As a lithium battery anode material, compared with a layered oxide anode material, the cation disordered oxide has higher specific capacity and better cycling stability. The research upgrades the cation disordered oxide into one of hot materials of the anode material of the lithium ion battery with high capacity and high energy density, and opens up a new direction for the research of the high-performance lithium ion battery. Recently, there has been a major breakthrough in the Nb-containing cation-disordered oxides due to Nb5+The redox reaction of the cations in the oxide can be stabilized. N. Yabuuchi et al vs. Li1.5Nb0.5O2Oxide cation (Ni)2+、Co2+、Mn3+、Fe3+Etc.) doping studies in which Li1.3Nb0.3Mn0.4O2The positive electrode material has larger reversible capacity, higher discharge voltage and excellent high-temperature charge and discharge performance.
Most of the reported cation disordered rock salt structure oxide cathode materials are synthesized by a traditional solid-phase sintering method, and the sintering temperature is higher than 1000 ℃ (under an inert atmosphere). High temperature solid phase reactions can lead to grain growth, compositional inhomogeneities, and possibly non-stoichiometric ratios due to volatilization of certain components. The sintering temperature required by the wet chemical method is far lower than that of the solid-phase sintering method, and the reaction process is easy to control. The wet chemical method can also reduce phase separation, avoid the generation of secondary phases, and the product has high purity and uniform grain size. Currently, there are a few Li for solid phase synthesis1.5Nb0.5O2The literature of the system oxide is reported, and no report is found in the relevant work of synthesizing the Nb-containing oxide cathode material by a wet chemical method. However, in the wet chemical method for synthesizing Nb-containing oxides, niobium precursor reagents such as niobium isopropoxide, niobium ethoxide, niobium chloride and the like are generally used. Niobium alkoxide precursors are relatively expensive and extremely sensitive to water vapor; niobium chloride is also relatively easy to hydrolyze and easily introduces chloride ion impurities.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a cathode material containing niobium/tantalum cation disordered rock salt structure.
A preparation method of a niobium/tantalum cation-containing disordered rock salt structure cathode material specifically comprises the following steps:
1) dissolving a transition metal salt in deionized water, and adding citric acid to form a transition metal salt solution A;
2) putting the niobium citrate/tantalum precursor solution into the solution A to form a mixed solution;
3) heating the solution obtained in the step 2) to dryness, and continuously drying to form a powder precursor;
4) pre-burning the powder precursor at low temperature, and then adding a proper amount of lithium salt for ball milling; and carrying out high-temperature annealing treatment after drying and compacting.
Further, the molar ratio of the transition metal salt to the citric acid in the step 1) is 1: 0.5-4, and the molar concentration of the transition metal salt is 0.2-2.0 mol/L.
Further, the transition metal salt in the step 1) is one or a mixture of more of Ni salt, Co salt, Mn salt, Mo salt or Cr salt; the transition metal salt is one or a mixture of more of nitrate, sulfate or acetate combined with metal ions; the transition metal salt may or may not contain water of crystallization.
Further, the transition metal Cr salt in the step 1) is ammonium chromate; the transition metal Mo salt is ammonium molybdate.
Further, the molar ratio of the niobium/tantalum ions in the step 2) to the transition metal salt ions in the solution A is 1: 0.5 to 3.
Further, the temperature for heating and drying in the step 3) is 70-90 ℃, the drying temperature is 100-180 ℃, and the drying time is 6-24 hours.
Further, the step 4) of the burn-in process is as follows: pretreating the powder precursor at the temperature of 300-400 ℃ for 1.0-3.0 hours;
the ball milling process comprises the following steps: mixing the pre-sintered powder with a proper amount of lithium salt, and ball-milling for 6-12 hours at a rotating speed of 300-500 r/min by using ethanol as a medium;
the annealing process comprises the following steps: annealing at 700-1000 ℃ for 6-24 hours.
Further, in the step 4), the lithium salt is one or a mixture of several of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, lithium sulfate and lithium chloride.
Further, the lithium salt in the step 4) is added in an amount satisfying Li1+xNbyTMzO2Or Li1+xTayTMzO2Wherein x + y + z is 1, x>0,y>0，z>0, wherein TM represents transition metal salt ions, such as nickel ions, cobalt ions, manganese ions, molybdenum ions or chromium ions; the lithium salt is added in an excess of 2-10 wt.% on the basis.
Further, the pre-sintering treatment and the annealing treatment in the step 4) are both carried out in a tubular furnace or a muffle furnace, and air or O is introduced at a flow rate of 20-600 mL/min2Or inert gas N2Or Ar.
The preparation method of the niobium and tantalum precursor solution in the step 2) obtains a Chinese invention patent, which is called as 'preparation method and application of stable water-soluble niobium and tantalum precursor', and is called as '200410014962.9'. The synthesis route for the water soluble niobium/tantalum precursor is: mixing niobium (tantalum) pentoxide and sodium hydroxide according to a molar ratio of 1: (2-20) mixing uniformly and grinding, and putting the mixture into a corundum crucible to be burnt for 2-4 hours at 400-550 ℃ (for example, burnt for 3 hours at 500 ℃), so as to obtain the sodium hydroxide melt of the niobium pentoxide (tantalum). Dissolving the melt in deionized water, adding proper amount of acetic acid into the filtered solution to regulate pH value, and precipitating white niobium (tantalum) acid. After filtration, the white precipitate was washed with deionized water several times to remove the residual sodium ions adsorbed therein. Finally, adding the niobium (tantalum) acid precipitate into a proper amount of citric acid aqueous solution, wherein the molar ratio of citric acid to niobium (tantalum) ions is (20-60): 1, dissolving niobium (tantalum) acid in a citric acid solution under the condition of heating and stirring at 60 ℃. After filtration, a stable aqueous solution of niobium (tantalum) citrate was obtained. The content of niobium (tantalum) in the solution can be calibrated by gravimetric method or plasma coupled resonance spectroscopy (ICP).
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention mainly aims at the problems of large crystal grains and uneven components caused by a solid-phase sintering method of the positive electrode material of the oxide containing the Nb/Ta cation disordered rock salt structure, high price of isopropanol niobium (tantalum), ethanol niobium (tantalum), niobium chloride (tantalum) and the like during liquid-phase synthesis, and is easy to hydrolyze;
(2) the invention synthesizes the oxide cathode material containing the Nb/Ta cation disordered rock salt structure for the first time by adopting a wet chemical method, the synthesis method is simple, the synthesized Nb/Ta oxide powder has high yield (about 100 percent), and the specific surface area of the product is larger and is about 5-20 m2The particles of the cathode material prepared by the method are in a nanometer level and have a porous structure, which is beneficial to Li in the charge and discharge process, as shown in figure 2+Shown in fig. 3, an electrochemical performance test shows that the first discharge capacity of the cathode material is up to 250mAh/g, the rate performance and the cycle performance are excellent, and the capacity retention rate after 100 cycles of 0.5C is more than 85%.
Drawings
FIG. 1 is a schematic diagram of a preparation process for synthesizing a niobium/tantalum cation-containing disordered rock salt structure cathode material;
FIG. 2 is Li in example 1 of the present invention1.3Nb0.3Mn0.4O2SEM image of the positive electrode material;
FIG. 3 is Li of example 1 of the present invention1.3Nb0.3Mn0.4O2100 cycle curves at 0.5C for Li button cells.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are further described in detail with reference to the accompanying drawings and specific embodiments.
Preparation example of the cathode material (the specific preparation process is shown in fig. 1):
synthesizing raw materials: niobium/tantalum citrate precursor solution, soluble nickel salt (analytical grade), soluble cobalt salt (analytical grade), soluble manganese salt (analytical grade), citric acid (analytical grade), deionized water.
Example one
Preparing a manganese nitrate solution with the cation concentration of 1.5mol/L, adding a proper amount of citric acid, wherein the molar ratio of metal manganese ions to the citric acid is 1: 1. adding a proper amount of water-soluble niobium citrate precursor solution, so that the molar ratio of the niobium ions to the transition manganese metal ions is Nb, TM is 1: 1.3. heating to evaporate the solution at 90 ℃, and drying at 150 ℃ for 12 hours to form a powder precursor; the powder precursor was pretreated at 350 ℃ for 2.0 hours. Mixing the pre-sintered powder with a proper amount of lithium salt, wherein the addition amount of the lithium salt needs to be 5 wt.%; ball milling is carried out for 6 hours at the rotating speed of 500r/min by taking ethanol as a medium. After drying and compacting, annealing for 12 hours at 850 ℃ in a tube furnace in Ar atmosphere to obtain Li1.3Nb0.3Mn0.4O2Cationic random oxide powder samples. The oxide material is used as a positive electrode material, a Li sheet is used as a counter electrode to assemble a button cell, and the discharge capacity is up to 263.7mAh/g under the conditions of room temperature, 1.5-4.8V and 20 mA/g; the retention after 100 cycles of 100mA/g was about 89.5%.
Example two
Preparing cobalt nitrate solution with cation concentration of 0.2mol/L, addingCitric acid, the molar ratio of metal cobalt ions to citric acid is 1: 0.5. adding a proper amount of water-soluble niobium citrate precursor solution, so that the molar ratio of the niobium ions to the metal cobalt ions is Nb, TM is 1: 0.5. heating to evaporate the solution at 70 ℃, and drying for 24 hours at 100 ℃ to form a powder precursor; the powder precursor was pretreated at 300 ℃ for 3.0 hours. Mixing the pre-sintered powder with a proper amount of lithium salt, wherein the addition amount of the lithium salt needs to be 10 wt.%; ball milling is carried out for 12 hours at the rotating speed of 300r/min by taking ethanol as a medium. After drying and compacting, N in a tube furnace2Annealing at 1000 deg.C for 6 hr under atmosphere to obtain Li1.25Nb0.5Co0.25O2Cationic random oxide powder samples. The oxide material is taken as a positive electrode material, a Li sheet is taken as a counter electrode to assemble a button cell, and the discharge capacity is up to 245.3mAh/g under the conditions of room temperature, 1.5-4.8V and 20 mA/g; the retention after 100 cycles of 100mA/g was about 85.6%.
EXAMPLE III
Preparing a nickel acetate solution with the cation concentration of 2.0mol/L, adding a proper amount of citric acid, wherein the molar ratio of metal nickel ions to the citric acid is 1: 4. adding a proper amount of water-soluble niobium citrate precursor solution, so that the molar ratio of niobium ions to metallic nickel ions is Nb, TM is 1: 3. heating to evaporate the solution at 80 ℃, and drying for 6 hours at 180 ℃ to form a powder precursor; the powder precursor was pretreated at 400 ℃ for 1.0 hour. Mixing the pre-sintered powder with a proper amount of lithium salt, wherein the addition amount of the lithium salt needs to be 2 wt.%; ball milling is carried out for 10 hours at the rotating speed of 400r/min by taking ethanol as a medium. After drying and compacting, in a tube furnace O2Annealing at 700 deg.C for 24 hr under atmosphere to obtain Li1.2Nb0.2Ni0.6O2A cationic disordered oxide material. The oxide material is taken as a positive electrode material, a Li sheet is taken as a counter electrode to assemble a button cell, and the discharge capacity is up to 221.3mAh/g under the conditions of room temperature, 1.5-4.6V and 20 mA/g; the retention after 100 cycles of 100mA/g was about 90.3%.
Example four
Preparing ammonium molybdate solution with cation concentration of 1.5mol/L, adding appropriate amount of citric acid, metal nickel ion and citric acidThe molar ratio is 1: 2. adding a proper amount of water-soluble tantalum citrate precursor solution to ensure that the molar ratio of tantalum ions to metal molybdenum ions is Ta: TM-3: 4. heating to evaporate the solution at 90 ℃, and drying for 8 hours at 150 ℃ to form a powder precursor; the powder precursor was pretreated at 400 ℃ for 2.0 hours. Mixing the pre-sintered powder with a proper amount of lithium salt, wherein the addition amount of the lithium salt needs to be 5 wt.%; ball milling is carried out for 10 hours at the rotating speed of 300r/min by taking ethanol as a medium. After drying and compacting, annealing for 12 hours at 850 ℃ in a tube furnace under the atmosphere of argon to obtain Li1.3Ta0.3Mo0.4O2A cationic disordered oxide material. The oxide material is used as a positive electrode material, a Li sheet is used as a counter electrode to assemble a button cell, and the discharge capacity is up to 256.1mAh/g under the conditions of room temperature, 1.5-4.8V and 20 mA/g; the retention after 100 cycles of 100mA/g was about 87.7%.
EXAMPLE five
Preparing a chromium nitrate mixed solution with the cation concentration of 1.5mol/L, adding a proper amount of citric acid, wherein the molar ratio of metal chromium ions to the citric acid is 1: 1. adding a proper amount of water-soluble tantalum citrate precursor solution to ensure that the molar ratio of tantalum ions to metal chromium ions is Ta: TM-1: 1. heating to evaporate the solution at 90 ℃, and drying for 8 hours at 150 ℃ to form a powder precursor; the powder precursor was pretreated at 400 ℃ for 2.0 hours. Mixing the pre-sintered powder with a proper amount of lithium salt, wherein the addition amount of the lithium salt needs to be 6 wt.%; ball milling is carried out for 12 hours at the rotating speed of 300r/min by taking ethanol as a medium. After drying and compacting, annealing for 12 hours at 900 ℃ in a muffle furnace under the air atmosphere to obtain Li1.2Nb0.4Cr0.4O2A cationic disordered oxide material. The oxide material is used as a positive electrode material, a Li sheet is used as a counter electrode to assemble a button cell, and the discharge capacity is up to 216.1mAh/g under the conditions of room temperature, 1.5-4.8V and 20 mA/g; the retention after 100 cycles of 100mA/g was about 83.7%.
EXAMPLE six
Preparing a manganese nitrate/cobalt nitrate mixed solution with the cation concentration of 1.0mol/L, wherein the molar ratio of manganese ions to cobalt ions is 1: 1. adding appropriate amount of citric acid, transition metal ion and fructus Citri LimoniaeThe molar ratio of the acid is 1: 1. adding a proper amount of water-soluble niobium citrate precursor solution, so that the molar ratio of niobium ions to other transition metal ions is Nb, TM is 1: 2. heating to evaporate the solution at 90 ℃, and drying for 8 hours at 150 ℃ to form a powder precursor; the powder precursor was pretreated at 400 ℃ for 2.0 hours. Mixing the pre-sintered powder with a proper amount of lithium salt, wherein the addition amount of the lithium salt needs to be 6 wt.%; ball milling is carried out for 8 hours at the rotating speed of 500r/min by taking ethanol as a medium. After drying and compacting, annealing for 12 hours at 900 ℃ in a muffle furnace under the air atmosphere to obtain Li1.3Nb0.3Co0.2Mn0.2O2Cationic random oxide material powder samples. The oxide material is used as a positive electrode material, a Li sheet is used as a counter electrode to assemble a button cell, and the discharge capacity is up to 211.5mAh/g under the conditions of room temperature, 1.5-4.8V and 20 mA/g; the retention after 100 cycles of 100mA/g was about 82.8%.
EXAMPLE seven
Preparing a manganese sulfate/cobalt sulfate/nickel sulfate mixed solution with a cation concentration of 1.5mol/L, wherein the molar ratio of manganese ions to cobalt ions is 2: 1. adding a proper amount of citric acid, wherein the molar ratio of the transition metal ions to the citric acid is 1: 2. adding a proper amount of water-soluble niobium citrate precursor solution, so that the molar ratio of niobium ions to other transition metal ions is Nb, TM is 1: 2. heating to evaporate the solution at 90 ℃, and drying for 8 hours at 150 ℃ to form a powder precursor; the powder precursor was pretreated at 400 ℃ for 2.0 hours. Mixing the pre-sintered powder with a proper amount of lithium salt, wherein the addition amount of the lithium salt needs to be 6 wt.%; ball milling is carried out for 10 hours at the rotating speed of 400r/min by taking ethanol as a medium. After drying and compacting, annealing for 12 hours at 950 ℃ in a tube furnace in air atmosphere to obtain Li1.2Nb0.3Ni0.2Co0.1Mn0.2O2Cationic random oxide material powder samples. The oxide material is used as a positive electrode material, a Li sheet is used as a counter electrode to assemble a button cell, and the discharge capacity is up to 218.8mAh/g under the conditions of room temperature, 1.5-4.8V and 20 mA/g; the retention after 100 cycles of 100mA/g was about 83.5%.
The foregoing is only a preferred embodiment of the present invention and appropriate changes and modifications may be made by those skilled in the art without departing from the principles of the invention and these changes and modifications are to be considered as the protection of the present invention.
Claims (8)
1. A preparation method of a niobium/tantalum cation-containing disordered rock salt structure cathode material is characterized by comprising the following steps:
1) dissolving a transition metal salt in deionized water, and adding citric acid, wherein the molar ratio of the transition metal salt to the citric acid is 1: 0.5-4, forming a transition metal salt solution A, wherein the transition metal salt is one or a mixture of more of Ni salt, Co salt, Mn salt, Mo salt or Cr salt;
2) putting the niobium/tantalum citrate precursor solution into the solution A, wherein the molar ratio of niobium/tantalum ions to transition metal salt ions in the solution A is 1: 0.5-3 to form a mixed solution;
3) heating the solution obtained in the step 2) to dryness, and continuously drying to form a powder precursor;
4) pre-sintering the powder precursor at 300-400 ℃, and then adding a proper amount of lithium salt for ball milling; and after drying and compacting, annealing at 700-1000 ℃.
2. The method for preparing the cathode material containing the niobium/tantalum cation disordered rock salt structure, according to claim 1, wherein the molar concentration of the transition metal salt in the step 1) is 0.2-2.0 mol/L.
3. The method for preparing the cathode material with the niobium/tantalum cation disordered rock salt structure as claimed in claim 1 or 2, wherein the transition metal salt in step 1) is one or a mixture of nitrate, sulfate or acetate combined with metal ions.
4. The method for preparing a cathode material containing a niobium/tantalum cation disordered rock salt structure, according to claim 1, wherein the transition metal Cr salt is ammonium chromate; the transition metal Mo salt is ammonium molybdate.
5. The preparation method of the niobium/tantalum cation-containing disordered rock salt structure cathode material as claimed in claim 1, wherein the temperature for heating and evaporating in the step 3) is 70-90 ℃, the drying temperature is 100-180 ℃, and the drying time is 6-24 hours.
6. The preparation method of the cathode material containing the niobium/tantalum cation disordered rock salt structure, which is characterized in that the pre-sintering treatment time in the step 4) is 1.0-3.0 hours;
the ball milling process comprises the following steps: mixing the pre-sintered powder with a proper amount of lithium salt, and ball-milling for 6-12 hours at a rotating speed of 300-500 r/min by using ethanol as a medium;
the annealing treatment time is 6-24 hours.
7. The method for preparing the cathode material with the niobium/tantalum cation disordered rock salt structure as claimed in claim 1, wherein the lithium salt in the step 4) is added in an amount satisfying Li1+xNbyTMzO2Or Li1+xTayTMzO2Wherein x + y + z is 1, x>0,y>0，z>0, wherein TM represents a transition metal salt ion; the lithium salt is added in an excess of 2-10 wt.% on the basis.
8. The preparation method of the niobium/tantalum cation-containing disordered rock salt structure cathode material as claimed in claim 1, wherein the pre-sintering treatment and the annealing treatment in the step 4) are carried out in a tube furnace or a muffle furnace, and air or O is introduced at a flow rate of 20-600 mL/min2Or inert gas N2Or Ar.
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Citations (4)
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| CN1699186A (en) * | 2004-05-21 | 2005-11-23 | 南京大学 | Preparation method of stable water-soluble niobium and tantalum precursor and application thereof |
| CN105742616A (en) * | 2016-02-29 | 2016-07-06 | 江苏大学 | Disordered rock salt structured lithium ion battery cathode material and preparation method thereof |
| CN107546384A (en) * | 2017-08-31 | 2018-01-05 | 江苏大学 | A kind of anode material for lithium-ion batteries of unordered rock salt structure and preparation method thereof |
| CN107925080A (en) * | 2015-08-26 | 2018-04-17 | 麻省理工学院 | For lithium rechargeable battery and the oxide of the cation disorder of other application |
-
2018
- 2018-09-10 CN CN201811055488.2A patent/CN109305700B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1699186A (en) * | 2004-05-21 | 2005-11-23 | 南京大学 | Preparation method of stable water-soluble niobium and tantalum precursor and application thereof |
| CN107925080A (en) * | 2015-08-26 | 2018-04-17 | 麻省理工学院 | For lithium rechargeable battery and the oxide of the cation disorder of other application |
| CN105742616A (en) * | 2016-02-29 | 2016-07-06 | 江苏大学 | Disordered rock salt structured lithium ion battery cathode material and preparation method thereof |
| CN107546384A (en) * | 2017-08-31 | 2018-01-05 | 江苏大学 | A kind of anode material for lithium-ion batteries of unordered rock salt structure and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Improvement of Cathode Properties by Lithium Excess in Disordered Rocksalt Li2+2xMn1−xTi1−xO4;Ayuko KITAJOU et al.;《Electrochemistry》;20160805;第8卷(第74期);第597-600页 * |
| 有序 /无序岩盐结构的 Li1+xM1－xO2锂离子电池正极材料;张联齐等;《化学进展》;20110331;第23卷(第2/3期);第410-417页 * |
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