CN114784269B - 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 PDF

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CN114784269B
CN114784269B CN202210694894.3A CN202210694894A CN114784269B CN 114784269 B CN114784269 B CN 114784269B CN 202210694894 A CN202210694894 A CN 202210694894A CN 114784269 B CN114784269 B CN 114784269B
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左宇轩
夏定国
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Abstract

The invention discloses a T2 type lithium cobaltate anode material with a space group of Cmca and a preparation method thereof. The chemical formula of the material is Li x Na y CoO 2 Wherein 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 anode material synthesized by the method 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; the specific capacity is also greatly improved compared with the mainstream commercial anode material in the existing market; and the synthesis method is simple and easy to implement and is convenient for industrial large-scale production.

Description

T2 type lithium cobaltate anode material with space group of Cmca and preparation method thereof
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 positive electrode 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 being capable of being repeatedly charged and discharged, the development has been over years, the application of the lithium ion battery relates to a plurality of fields such as traffic, entertainment, military, medical treatment and communication, and the like, and 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 popularized. The main factor for limiting the specific energy density of the battery is the anode material, and several mainstream materials O3-LiCoO on the market 2 （140 mAh/g）、LiFePO 4 （160 mAh/g）、LiMn 2 O 4 The specific capacity of (150 mAh/g) is lower than 200 mAh/g, and the lithium-rich manganese-based positive electrode xLi can meet the high capacity requirement 2 MnO 3 ·（1-x）LiMO 2 The 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-Li x MO 2 (M = Co, Ni, Mn, Fe) was reported as early as 1999 (Journal of The Electrochemical Society, 146 (10) 3560-3565 (1999)), but this phase was only reported during Electrochemical cyclingFormed in the process. The T2 type layered lithium cobaltate lithium ion battery positive electrode material has the structural characteristic 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 lithium is greatly different from the lithium of an octahedral site in the traditional commercialized O3 type lithium cobaltate.
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 spectrometer x Na y CoO 2 Wherein 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), since the present material is prepared by an ion exchange method, sodium ions are hardly completely exchanged with lithium ions, and thus a small part of very small amount of sodium ions may 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 unit cell through neutron diffraction, and finds that lithium ions occupy the 8e position, cobalt ions occupy the 4a position, oxygen ions occupy the 8f position, and the space group attribution is also Cmca. The neutron diffraction result and the X-ray diffraction result are consistent in judgment of space groups, and the result shows that lithium ions in the material form tetrahedrons with adjacent oxygen around, namely 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 specifically 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 Na 2 CO 3 Dissolving 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 Na x CoO 2 (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 Na x CoO 2 （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 obtaining a final product, namely the T2 type lithium cobaltate layered positive electrode 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 solution 2 CO 3 As a precipitant, in an amount 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 Na x CoO 2 (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 an appropriate amount of ethanol or acetone, ball-milling for a period of time, grinding the obtained mixture, calcining for 3-6 h at 400-500 ℃ firstly, and calcining for 8-16 h at 600-900 ℃ to obtain a P2 type precursor Na x CoO 2 ；
2b, performing the P2 type precursor Na obtained in the step 2a x CoO 2 And carrying out ion exchange reaction with 2.5-10 times of the molar amount of lithium salt at 80-300 ℃ for 2-8 hours to obtain a product, filtering, washing and drying the product to obtain the T2 type lithium cobaltate layered positive electrode material.
In step 2a, the cobalt salt is selected from one or more of cobaltous oxide, cobaltosic oxide and cobalt hydroxide.
In the step 2a, the ball milling 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 is up to 230 mAh/g under 135 mA/g rate in a 3-4.55V interval; specific capacity is compared withThe commercial anode material O3-LiCoO which is mainstream on the market 2 The (190 mAh/g) is greatly improved. 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 invention 0.72 CoO 2 Scanning electron micrograph (c).
FIG. 2 shows the lithium cobaltate cathode material Li of T2 type lithium ion battery prepared in example 2 of the present invention 0.7 Na 0.02 CoO 2 Scanning electron micrograph (c).
FIG. 3 shows the lithium cobaltate cathode material Li of T2 type lithium ion battery prepared in example 2 of the present invention 0.7 Na 0.02 CoO 2 X-ray diffraction pattern of (a).
FIG. 4 shows the lithium cobaltate cathode material Li of T2 type lithium ion battery prepared in example 2 of the present invention 0.7 Na 0.02 CoO 2 Neutron diffraction profile (numbers on the peak represent corresponding crystallographic plane indices).
FIG. 5 shows the lithium cobaltate cathode material Li of T2 type lithium ion battery prepared in example 2 of the present invention 0.7 Na 0.02 CoO 2 Schematic diagram of theoretical structure of (1).
FIG. 6 shows the lithium cobaltate cathode material Li of T2 type lithium ion battery prepared in example 2 of the present invention 0.7 Na 0.02 CoO 2 A 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 invention 0.7 Na 0.02 CoO 2 Cycling 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 method 0.7 Na 0.02 CoO 2
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, and grinding uniformlyThen placing the mixture in a tube furnace, presintering the mixture for 4 hours at 450 ℃, and then calcining the mixture for 8 hours at 800 ℃ to obtain a precursor product Na containing sodium 0.72 CoO 2 。
Mixing the sodium-containing precursor with 5 times of molar weight of lithium salt LiNO 3 Ion 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-Li 0.7 Na 0.02 CoO 2 。
The T2-Li prepared by the method 0.7 Na 0.02 CoO 2 Mixing with carbon black and PVDF (polyvinylidene fluoride) in a mass ratio of 8:1:1, grinding uniformly by using N-methyl pyrrolidone as a solvent, then coating on an aluminum foil, and placing in a forced air drying oven to dry for 24 hours at 100 ℃. After taking out, the electrode wafer is cut after rolling on a rolling machine for several times. The lithium ion battery 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-pressure electrolyte of a lithium ion battery produced by Beijing chemical reagent research institute, a button battery is arranged in a glove box, and the temperature is 25 ℃ at room temperature by testing on a Xinwei battery testing system.
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 2T 2 configuration binary lithium-rich material Li synthesized by coprecipitation method and ion exchange method 0.7 Na 0.02 CoO 2
0.12 mol of CoSO is taken 4 ·6H 2 Dissolving O in 60 mL of deionized water, stirring uniformly to obtain a salt solution, and then taking 0.12 mol of Na 2 CO 3 And 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) dropwise adding the prepared alkali solution and the prepared salt solution into deionized water by using a peristaltic pump at the same time, keeping the pH value between 7.5 and 8.5, heating in a water bath at the temperature of 60 ℃, and stirring continuously 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 precipitate obtained by filtering in a vacuum oven at 80 ℃ for more than 8 h, and then grinding to obtain a precursor carbonate CoCO 3 。
Taking 1.15 g of precursor carbonate and 0.371 g of Na 2 CO 3 Uniformly 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 Na 0.72 CoO 2 Product, Na 0.72 CoO 2 The scanning electron micrograph of (a) is shown in FIG. 1.
Mixing the sodium-containing precursor with 5 times of molar weight of lithium salt LiNO 3 Ion 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 Li 0.7 Na 0.02 CoO 2 。
Product Li 0.7 Na 0.02 CoO 2 The 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 fig. 3, and is characterized in that the main peak 002 is between 17.9 and 18.1 degrees, and has a strong 131 diffraction peak at 67.5 degrees, the space group is Cmca, and the crystal cell belongs to the cubic system, and the three rotation angles 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 Li 0.7 Na 0.02 CoO 2 The positions and the proportions of the atoms of the lithium ion complex can be found to be 8e, 4a and 8f, respectively, of the lithium ion, the space group assignment is also Cmca, which is consistent with the XRD result, and the lithium and the surrounding oxygen form tetrahedron, that is, the lithium ion occupies tetrahedral position, which is greatly different from the octahedral position lithium ion of the traditional lithium cobaltate. This gave Li as the T2-type material 0.7 Na 0.02 CoO 2 Fig. 5 shows a theoretical structure model diagram of (a).
Figure 968640DEST_PATH_IMAGE001
The product Li 0.7 Na 0.02 CoO 2 Mixing 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, when the voltage range of the synthesized anode material is between 3.0 and 4.55V (figure 6) and the current density is 135 mA/g, the first discharge capacity is 220 mAh/g (figure 7).

Claims (8)

1. The positive electrode material of the lithium ion battery is characterized in that a P2 type precursor Na is used as the material x CoO 2 The T2 type lithium cobaltate layered positive electrode material is synthesized by ion exchange reaction of lithium nitrate with 2.5-10 times of molar weight at 80-300 ℃ for 2-8 hours, and the component is Li x Na y CoO 2 Wherein 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 attribution is Cmca and belongs to a cubic crystal system; the material has three structural features: 1) the lithium ions form tetrahedra with adjacent oxygen; 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 stoichiometric ratio of equimolar cobalt and carbonate, cobalt salt is dissolved in deionized water to preparePreparing a salt solution with the concentration of 0.5-2 mol/L; mixing Na 2 CO 3 Dissolving 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 Na x CoO 2 Uniformly 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 Na x CoO 2 Wherein x is more than or equal to 0.6 and less than or equal to 1;
1e) the precursor Na of P2 type x CoO 2 And carrying out ion exchange reaction with 2.5-10 times of the molar weight of lithium nitrate at 80-300 ℃ for 2-8 hours, filtering, washing and drying the obtained product, thus obtaining the T2 type lithium cobaltate layered positive electrode 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 of claim 3, wherein in step 1 b), 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.
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. A method for preparing the lithium ion battery cathode material of claim 1 or 2, which comprises the following steps:
2a) according to the formula Na x CoO 2 The stoichiometric ratio of cobalt to sodium shown in the specification is that cobalt salt and sodium carbonate are mixed, ethanol or acetone is added for ball milling, the obtained mixture is ground and then calcined at 400-500 ℃ for 3-6 h, and then calcined at 600-900 ℃ for 8-16 h to obtain a P2 type precursor Na x CoO 2 Wherein x is more than or equal to 0.6 and less than or equal to 1;
2b) the precursor Na of P2 type x CoO 2 And carrying out ion exchange reaction with 2.5-10 times of the molar weight of lithium nitrate at 80-300 ℃ for 2-8 hours to obtain a product, filtering, washing and drying to obtain the T2 type lithium cobaltate layered cathode material.
8. The method of claim 7, 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.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101689631A (en) * 2007-06-25 2010-03-31 三洋电机株式会社 Nonaqueous electrolyte secondary battery and manufacturing method of cathode
KR20160093854A (en) * 2015-01-30 2016-08-09 주식회사 엘 앤 에프 Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same

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CN108023082B (en) * 2017-12-04 2021-04-16 中南大学 Preparation method of sodium-ion battery positive electrode material with multiphase composite layered structure
CN113991079A (en) * 2021-10-20 2022-01-28 陈琴雅 Composite cathode material and preparation method thereof
CN114613992A (en) * 2022-03-25 2022-06-10 珠海冠宇电池股份有限公司 Positive electrode material, battery and electronic equipment
CN114784269B (en) * 2022-06-20 2022-09-27 北京大学 T2 type lithium cobalt oxide positive electrode material with space group of Cmca and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101689631A (en) * 2007-06-25 2010-03-31 三洋电机株式会社 Nonaqueous electrolyte secondary battery and manufacturing method of cathode
KR20160093854A (en) * 2015-01-30 2016-08-09 주식회사 엘 앤 에프 Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same

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