CN114784269A - T2 type lithium cobalt oxide positive electrode material with space group of Cmca and preparation method thereof - Google Patents
T2 type lithium cobalt oxide positive electrode material with space group of Cmca and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a T2 type lithium cobalt oxide anode material with a space group of Cmca and a preparation method thereof. The chemical formula of the material is LixNayCoO2Wherein x is more than or equal to 0.6 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.1; the lithium ion forms tetrahedral coordination with the adjacent oxygen ion; the main peak of the X-ray diffraction pattern is 17.9-18.1 degrees, and the strong 131 crystal face diffraction peak is in 67.0-67.5 degrees, and belongs to the Cmca space group characteristic peak. Firstly synthesizing a precursor P2 phase layered sodium cobaltate by a solid phase ball milling method or a coprecipitation method, and then obtaining the T2 configuration lithium cobaltate layered positive electrode material by ion exchange. The synthesized positive electrode material has uniform particles and high crystallinity; the first coulombic efficiency is 125%; the cycle performance and the rate performance are very excellent, and the reversible capacity under 135 mA/g rate is up to 230 mAh/g; specific capacity is compared withThe commercial anode material which is mainstream in the market is also greatly improved; and the synthesis method is simple and easy to implement and is convenient for industrial large-scale production.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials and electrochemistry, and particularly relates to a T2 type lithium cobaltate layered anode material with a space group of Cmca prepared by an ion exchange method.
Background
The lithium ion battery is a secondary battery with the characteristic of repeated charge and discharge, has been developed for years, and the application of the lithium ion battery relates to traffic, entertainment, military affairs and medical scienceIn the fields of treatment, communication and the like, the lithium ion battery electric automobile developed in recent years has a very high application prospect due to the environmental friendliness. However, the specific energy density of the battery is limited, so that the electric vehicle cannot meet the requirements of most users, and is not widely used. The main factor for limiting the specific energy density of the battery is the anode material, and several mainstream materials O3-LiCoO on the market2（140 mAh/g）、LiFePO4（160 mAh/g）、LiMn2O4The specific capacity of (150 mAh/g) is lower than 200 mAh/g, and the lithium-rich manganese-based positive electrode xLi meeting the high capacity requirement2MnO3·（1-x）LiMO2The problem of voltage decline of (250 mAh/g) can not be solved well in time, so that the search for a lithium battery positive electrode material with high energy density and stable structure is an important task in the current lithium battery research field.
T2-LixMO2(M = Co, Ni, Mn, Fe) was reported earlier in 1999 (Journal of The Electrochemical Society, 146 (10) 3560-3565 (1999)), however this phase only formed during Electrochemical cycling. The structure of the T2 type layered lithium cobalt oxide lithium ion battery anode material is characterized in that oxygen atom layers are periodically arranged by taking the distance between two transition metal layers as a period, wherein lithium is positioned at a tetrahedral site, and the anode material is greatly different from lithium at an octahedral site in the traditional commercialized O3 type lithium cobalt oxide.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a layered lithium ion battery anode material with ultrahigh stability and rate capability and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme: the positive electrode material of the lithium ion battery is a T2 type lithium cobaltate layered positive electrode material synthesized by an ion exchange method, and the detection component of the positive electrode material is Li by an inductively coupled plasma spectrometerxNayCoO2Wherein 0.6. ltoreq. x.ltoreq.1, 0. ltoreq. y.ltoreq.0.1 (preferably, 0.6. ltoreq. x.ltoreq.0.8, 0. ltoreq. y.ltoreq.0.05), because the material is prepared by an ion exchange method, a part of residual sodium ions are presentIt is difficult to completely exchange lithium ions, so a small fraction of very small amounts of sodium ions will be present in the material. The X-ray diffraction pattern (copper target, wavelength is 1.54 angstrom) of the material is characterized in that a main peak 002 is between 17.9 and 18.1 degrees, and a strong 131 diffraction peak is provided at 67.0 to 67.5 degrees, a space group is represented as Cmca, the material belongs to a cubic system, three corners of a unit cell are alpha = beta = gamma =90 degrees, and the traditional O3 type lithium cobaltate belongs to a hexagonal system. Because neutron diffraction is more sensitive to the occupation of light elements, the invention further refines the occupation distribution of each atom in the crystal cell through neutron diffraction, and finds that lithium ions occupy a position of 8e, cobalt ions occupy a position of 4a, oxygen ions occupy a position of 8f, and the space group attribution is also Cmca. The neutron diffraction result and the X-ray diffraction result are consistent with the judgment of the space group, and the result shows that the lithium ions in the material form tetrahedrons with the adjacent oxygen around, that is, the lithium ions occupy tetrahedral positions, which is greatly different from octahedral position lithium ions of the traditional lithium cobaltate.
The preparation method of the layered Cmca phase lithium ion battery anode material comprises the following two steps:
(1) coprecipitation method + ion exchange method
1a, dissolving cobalt salt in deionized water according to the equimolar stoichiometric ratio of cobalt and carbonate to prepare a salt solution with the concentration of 0.5-2 mol/L, and adding Na2CO3Dissolving the aqueous solution and ammonia water in deionized water to prepare an aqueous alkali with the pH value of 7-9;
1b, respectively and simultaneously dripping the alkali solution and the salt solution into a container filled with deionized water at a constant speed, wherein the pH value in the whole process is controlled to be 7-9, and the temperature is controlled to be 50-80 ℃;
1c, standing and aging at 50-80 ℃ for 8-16 h after the dropwise addition is finished, then filtering, washing, drying and precipitating to obtain a precursor cobalt carbonate;
1d according to the formula NaxCoO2(x is more than or equal to 0.6 and less than or equal to 1) uniformly grinding a compound of a precursor cobalt carbonate and sodium at a stoichiometric ratio of cobalt to sodium, pre-burning the mixture at 400-500 ℃ for 3-10 h, and then calcining the mixture at 600-1000 ℃ for 8-16 h to obtain an intermediate product, namely a P2 type precursor NaxCoO2（0.6 ≤ x ≤ 1）；
And 1e, carrying out ion exchange reaction on the mixture of the intermediate product obtained in the step 1d and lithium salt with the molar weight of 2.5-10 times at the temperature of 80-300 ℃ for 2-8 hours, filtering, washing and drying the obtained product, and thus obtaining a final product, namely the T2 type lithium cobaltate layered cathode material.
In step 1a, the cobalt salt is preferably one or more selected from cobalt sulfate, cobalt nitrate and cobalt chloride.
In step 1a, Na is contained in the alkali solution2CO3As a precipitant, an amount of the substance of (a) is twice that of the cobalt salt; and ammonia water is used as a buffering agent to control the pH value of the solution to be 7-9.
In the step 1b, the alkali solution and the salt solution are respectively added into a container containing deionized water at a constant speed by a peristaltic pump, and the dropping speed is controlled to be 0.8-1.8 mL/min.
In the step 1d, the sodium compound is selected from one or more of sodium hydroxide, sodium carbonate, sodium acetate and sodium nitrate, and the dosage of the sodium compound is 0.6-1 time of the molar amount of the precursor cobalt carbonate.
In step 1e, the lithium salt is selected from one or more of lithium hydroxide, lithium carbonate, lithium chloride and lithium nitrate.
(2) Ball milling + ion exchange method
2a, according to the formula NaxCoO2(x is more than or equal to 0.6 and less than or equal to 1) according to the stoichiometric ratio of cobalt to sodium, mixing cobalt salt and sodium carbonate, adding appropriate amount of ethanol or acetone, ball milling for a period of time, grinding the obtained mixture, calcining for 3-6 hours at 400-500 ℃ firstly, and calcining for 8-16 hours at 600-900 ℃ to obtain a P2 type precursor NaxCoO2；
2b, performing the P2 type precursor Na obtained in the step 2axCoO2And carrying out ion exchange reaction with 2.5-10 times of the molar weight of lithium salt at 80-300 ℃ for 2-8 hours to obtain a product, filtering, washing and drying to obtain the T2 type lithium cobalt oxide layered positive electrode material.
In step 2a, the cobalt salt is selected from one or more of cobaltous oxide, cobaltous oxide and cobalt hydroxide.
In the step 2a, the ball milling rotation speed is preferably 100-500 rpm, and the ball milling time is 1-8 h.
In step 2b, the lithium salt is selected from one or more of lithium hydroxide, lithium carbonate, lithium chloride and lithium nitrate.
Compared with the prior art, the invention has the beneficial effects that:
the invention firstly synthesizes a precursor P2 phase layered sodium cobaltate by a solid phase ball milling method or a coprecipitation method, and then carries out low-temperature ion exchange by an ion exchange reaction to obtain the brand-new T2 type lithium cobaltate layered anode material. The material has three structural features: (1) the lithium ion forms tetrahedral coordination with the adjacent oxygen ion; (2) the main peak 002 of the X-ray diffraction pattern of the material is between 17.9 and 18.1 degrees; (3) the X-ray diffraction pattern of the material has a strong 131 crystal plane diffraction peak within 67.0-67.5 degrees, and belongs to a Cmca space group characteristic peak. The first coulombic efficiency of the T2 type laminar lithium cobalt oxide anode material synthesized by the method is 125%; the cycle performance and the rate capability are very excellent, and the reversible capacity under 135 mA/g rate in a 3-4.55V interval is up to 230 mAh/g; compared with the mainstream commercial anode material O3-LiCoO on the existing market in specific capacity2There was a dramatic increase in (190 mAh/g). The method for synthesizing the T2 type lithium ion battery anode material is simple and easy to implement, is convenient for industrial large-scale production, and the synthesized product has uniform particles and high crystallinity.
Drawings
FIG. 1 shows a lithium cobaltate cathode material precursor P2-Na of a lithium ion battery prepared in example 2 of the present invention0.72CoO2Scanning electron microscope image (c).
FIG. 2 shows the lithium cobaltate cathode material Li of T2 type lithium ion battery prepared in example 2 of the present invention0.7Na0.02CoO2Scanning electron microscope image (c).
FIG. 3 shows the lithium cobaltate cathode material Li of T2 type lithium ion battery prepared in example 2 of the present invention0.7Na0.02CoO2X-ray diffraction pattern of (a).
FIG. 4 shows the lithium cobaltate cathode material Li of the T2 type lithium ion battery prepared in example 2 of the invention0.7Na0.02CoO2Neutron diffraction profile (numbers on the peak represent corresponding crystallographic planes and indicateNumber).
FIG. 5 shows the lithium cobaltate cathode material Li of T2 type lithium ion battery prepared in example 2 of the present invention0.7Na0.02CoO2Schematic diagram of theoretical structure of (1).
FIG. 6 shows the lithium cobaltate cathode material Li of the T2 type lithium ion battery prepared in example 2 of the invention0.7Na0.02CoO2A charge-discharge curve under 135 mA/g multiplying power.
FIG. 7 shows the lithium cobaltate cathode material Li of T2 type lithium ion battery prepared in example 2 of the present invention0.7Na0.02CoO2Cycling performance at 135 mA/g rate.
Detailed Description
Example 1 Synthesis of binary lithium-rich material Li with T2 configuration by ball milling method and ion exchange method0.7Na0.02CoO2
1.8732 g of cobaltous oxide and 0.954g of sodium carbonate are taken, 5 mL of ethanol is added, ball milling and mixing are carried out for 4 hours at the rotating speed of 300 rpm, and then drying is carried out. Taking out the dried mixed precursor, grinding uniformly, placing in a tubular furnace, presintering for 4 hours at 450 ℃, and calcining for 8 hours at 800 ℃ to obtain a sodium-containing precursor product Na0.72 CoO2。
Mixing the sodium-containing precursor with 5 times of molar weight of lithium salt LiNO3Ion exchange is carried out for 0.5 h at 280 ℃, the obtained sample is washed for 2 times by deionized water and then dried in a blast oven at 100 ℃ to obtain the final sample T2-Li0.7Na0.02CoO2。
The T2-Li prepared by the method0.7Na0.02CoO2Mixing with carbon black and PVDF (polyvinylidene fluoride) in a mass ratio of 8:1:1, grinding uniformly by using N-methylpyrrolidone as a solvent, coating on an aluminum foil, and placing in a forced air drying oven for drying at 100 ℃ for 24 hours. After taking out, the electrode wafer is cut after rolling on a rolling machine for several times. The lithium cell is used as a positive plate, a lithium plate is used as a negative plate, glass microfiber filter paper GF/D produced by Whatman company is used as a battery diaphragm, electrolyte is high-voltage electrolyte of a lithium ion battery produced by Beijing chemical reagent research institute, a button cell is arranged in a glove box, and a Xinwei battery testing system is arrangedThe temperature of the above test was 25 ℃.
Under the condition, when the voltage range of the anode material is 3.0-4.55V and the current density is 135 mA/g, the initial discharge capacity is 230 mAh/g.
Example 2 coprecipitation method + ion exchange method synthesized T2 configuration binary lithium-rich material Li0.7Na0.02CoO2
0.12 mol of CoSO is taken4·6H2Dissolving O in 60 mL of deionized water, stirring uniformly to obtain a salt solution, and then taking 0.12 mol of Na2CO3And 2 mL of an aqueous ammonia solution having a concentration of 18.4 mol/L, and water was added thereto to prepare 60 mL of an aqueous alkali solution. And (3) simultaneously dropwise adding the prepared alkali solution and salt solution into deionized water by using a peristaltic pump, keeping the pH value between 7.5 and 8.5, heating in a water bath at the temperature of 60 ℃, and continuously stirring at the stirring speed of 500 rpm.
And standing and aging the obtained suspension for more than 12 h after the dropwise addition is finished, then filtering the suspension by using a Buchner funnel, and washing the suspension for more than 3 times by using deionized water. Drying the filtered precipitate in a vacuum oven at 80 ℃ for more than 8 h, and grinding to obtain a precursor carbonate CoCO3。
Taking 1.15 g of precursor carbonate and 0.371 g of Na2CO3Uniformly mixing and grinding, placing in a tube furnace for presintering at 500 ℃ for 4 h, then calcining at 800 ℃ for 8 h, taking out and grinding to obtain a powder sample which is a sodium-containing precursor Na0.72CoO2Product, Na 0.72CoO2The scanning electron micrograph of (a) is shown in FIG. 1.
Mixing the sodium-containing precursor with 5 times of molar weight of lithium salt LiNO3Ion exchange is carried out for 0.5 h at 280 ℃, the obtained sample is washed for 2 times by deionized water and then dried in a blast oven at 100 ℃ to obtain the final sample Li0.7Na0.02CoO2。
Product Li0.7Na0.02CoO2The scanning electron micrograph of (A) is shown in FIG. 2, and it can be seen that the particle diameter is about 5 μm. The XRD pattern is shown in figure 3, and is characterized in that the main peak 002 is between 17.9 and 18.1 degrees, and the strong 131 diffraction peak is provided at 67.5 degrees, and the space groupAssigned Cmca, belonging to the cubic system, the three rotation angles of the unit cell α = β = γ =90 °.
Since neutron diffraction is more sensitive to occupancy of the light element, we further refine the occupancy distribution of the atoms in the cell by neutron diffraction, as shown in fig. 4. Table 1 shows Li0.7Na0.02CoO2The position and the proportion of each atom of (a) can be found that lithium ions occupy the 8e position, cobalt ions occupy the 4a position, oxygen ions occupy the 8f position, the space group assignment is also Cmca, which is consistent with the XRD result, and lithium and surrounding oxygen form tetrahedrons, that is, lithium ions occupy tetrahedral positions, which is greatly different from octahedral position lithium ions of the traditional lithium cobaltate. This gave Li as the T2 type material0.7Na0.02CoO2Fig. 5 shows a theoretical structure model diagram of (1).
The product Li0.7Na0.02CoO2Mixing the carbon black and PVDF in a mass ratio of 8:1:1, grinding the mixture uniformly by using N-methyl pyrrolidone as a solvent, then coating the mixture on an aluminum foil, placing the aluminum foil on a forced air drying oven to dry for 1 hour at 100 ℃, taking out the aluminum foil, rolling the aluminum foil on a roller press for several times, and cutting the aluminum foil into electrode wafers. The electrode wafer is used as a positive plate, a lithium plate is used as a negative plate, glass microfiber filter paper GF/D produced by Whatman company is used as a battery diaphragm, high-voltage electrolyte of a lithium ion battery produced by Beijing chemical reagent research institute is used as the electrolyte of the battery, the battery is assembled into a button cell in a glove box and tested on a Xinwei battery testing system at the room temperature of 25 ℃.
Under the condition, the synthesized anode material has the first discharge capacity of 220 mAh/g (figure 7) when the voltage range is between 3.0 and 4.55V (figure 6) and the current density is 135 mA/g.
Claims (10)
1. The anode material of the lithium ion battery is characterized in that the anode material is a T2 type lithium cobaltate layered anode material synthesized by an ion exchange method, and the component is LixNayCoO2Which isWherein x is more than or equal to 0.6 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.1, and the space group is Cmca and belongs to a cubic crystal system; the material has three structural features: 1) the lithium ions form tetrahedrons with adjacent oxygens; 2) the main peak of the X-ray diffraction pattern of the material is 17.9-18.1 degrees; 3) the X-ray diffraction pattern of the material has a strong 131 crystal plane diffraction peak within 67.0-67.5 degrees, and belongs to a Cmca space group characteristic peak.
2. The positive electrode material for lithium ion batteries according to claim 1, wherein x is 0.6. ltoreq. x.ltoreq.0.8, and y is 0. ltoreq. y.ltoreq.0.05.
3. A method for preparing the lithium ion battery cathode material of claim 1 or 2, which comprises the following steps:
1a) according to the equimolar stoichiometric ratio of cobalt and carbonate, dissolving cobalt salt in deionized water to prepare a salt solution with the concentration of 0.5-2 mol/L; na is mixed with2CO3Dissolving the aqueous solution and ammonia water in deionized water to prepare an aqueous alkali with the pH value of 7-9;
1b) respectively and simultaneously dripping the aqueous alkali and the salt solution prepared in the step 1 a) into a container filled with deionized water at a constant speed, wherein the pH value in the whole process is controlled to be 7-9, and the temperature is 50-80 ℃;
1c) standing and aging at 50-80 ℃ for 8-16 h after the dropwise addition is finished, and then filtering, washing, drying and precipitating to obtain a precursor cobalt carbonate;
1d) according to the formula NaxCoO2Uniformly grinding a precursor compound of cobalt carbonate and sodium at the stoichiometric ratio of cobalt to sodium, pre-sintering at 400-500 ℃ for 3-10 h, and then calcining at 600-1000 ℃ for 8-16 h to obtain a P2 type precursor NaxCoO2Wherein x is more than or equal to 0.6 and less than or equal to 1;
1e) the P2 type precursor NaxCoO2And carrying out ion exchange reaction on the mixture with 2.5-10 times of the molar weight of lithium salt for 2-8 hours at the temperature of 80-300 ℃, filtering, washing and drying the obtained product, thus obtaining the T2 type lithium cobalt oxide layered anode material.
4. The method of claim 3, wherein in step 1 a), the cobalt salt is selected from one or more of cobalt sulfate, cobalt nitrate, and cobalt chloride.
5. The method as claimed in claim 3, wherein in step 1 b), the alkaline solution and the salt solution are respectively added into the container with the deionized water at a constant speed by a peristaltic pump, and the dropping speed is controlled to be 0.8-1.8 mL/min.
6. The method of claim 3, wherein in step 1 d), the sodium compound is selected from one or more of sodium hydroxide, sodium carbonate, sodium acetate, and sodium nitrate.
7. The method of claim 3, wherein in step 1 e), the lithium salt is selected from one or more of lithium hydroxide, lithium carbonate, lithium chloride, and lithium nitrate.
8. A method for preparing the lithium ion battery positive electrode material of claim 1 or 2, which is characterized by comprising the following steps:
2a) according to the formula NaxCoO2Mixing cobalt salt and sodium carbonate according to the stoichiometric ratio of cobalt to sodium shown in the specification, adding ethanol or acetone for ball milling, grinding the obtained mixture, calcining for 3-6 h at 400-500 ℃, calcining for 8-16 h at 600-900 ℃ to obtain a P2 type precursor NaxCoO2Wherein x is more than or equal to 0.6 and less than or equal to 1;
2b) the precursor Na of P2 typexCoO2And carrying out ion exchange reaction on the mixture of the lithium salt and 2.5-10 times of the molar weight of the mixture at the temperature of 80-300 ℃ for 2-8 hours to obtain a product, and filtering, washing and drying the product to obtain the T2 type lithium cobaltate layered cathode material.
9. The method of claim 8, wherein in step 2 a) the cobalt salt is selected from one or more of cobaltous oxide, cobaltous hydroxide; the ball milling speed is 100-500 rpm, and the ball milling time is 1-8 h.
10. The method of claim 8, wherein in step 2 b), the lithium salt is selected from one or more of lithium hydroxide, lithium carbonate, lithium chloride, and lithium nitrate.
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| PCT/CN2022/118030 WO2023245880A1 (en) | 2022-06-20 | 2022-09-09 | T2-type lithium cobalt oxide positive electrode material with space group of cmca and preparation method therefor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023245880A1 (en) * | 2022-06-20 | 2023-12-28 | 北京大学 | T2-type lithium cobalt oxide positive electrode material with space group of cmca and preparation method therefor |
| WO2024045937A1 (en) * | 2022-09-02 | 2024-03-07 | 珠海冠宇电池股份有限公司 | Positive electrode active material and use thereof |
| WO2024153145A1 (en) * | 2023-01-17 | 2024-07-25 | 珠海冠宇电池股份有限公司 | Positive electrode material and battery comprising same |
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| WO2024045937A1 (en) * | 2022-09-02 | 2024-03-07 | 珠海冠宇电池股份有限公司 | Positive electrode active material and use thereof |
| WO2024153145A1 (en) * | 2023-01-17 | 2024-07-25 | 珠海冠宇电池股份有限公司 | Positive electrode material and battery comprising same |
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| CN114784269B (en) | 2022-09-27 |
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