CN114242976A - Preparation method of fluoride modified lithium cobaltate positive electrode material - Google Patents
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Abstract
The invention relates to a preparation method of a fluoride modified lithium cobaltate positive electrode material, which comprises the following steps: (1) mixing cobalt oxyhydroxide and lithium in a certain ratio by a jar mill, roasting at 1000 ℃, and carrying out post-treatment on the roasted material to obtain small-particle single crystal lithium cobaltate; (2) mixing AlCl3·6H2O, LiCl and NH4And F is completely dissolved in deionized water, then 15g of lithium cobaltate is slowly added into the solution, the solution is heated and stirred, the mixed solution is poured into a PTFE high-pressure hydrothermal reaction kettle, and drying treatment is carried out in a forced air drying oven to obtain the matrix material. (3) And sintering the base material, and treating the sintered material to obtain the fluoride modified lithium cobaltate cathode material. The preparation method has the advantages that firstly, the lithium fluoride and the aluminum fluoride obtain double-coating effect; second, lithium cobaltate surface coatingThe Co-cladding modification can effectively promote the formation of Co-Al-O-F substances, and the substances can effectively inhibit the side reaction of electrolyte and reduce the surface impedance accumulation of materials under high voltage.
Description
Technical Field
The invention relates to the field of battery anode materials, in particular to a preparation method of a fluoride modified lithium cobaltate anode material.
Background
The traditional method for preparing lithium cobaltate has been commercialized as early as many years ago, gradually occupies the market of traditional 3C, and how to effectively release more capacity of lithium cobaltate at present is a problem which is commonly solved by all the requirements of traditional 3C products and technical research and development personnel. The technical route for solving the problem is to select a liquid-phase coprecipitation method to dope salt solutions of Al, Mg, Ti and the like, or to coat metal oxides and carbon by a solid-phase sintering method. But the method has the defects of difficult industrialization, high process preparation requirement, complex technical difficulty and difficult guarantee of product consistency.
At present, the preparation route of the lithium cobaltate for industrial industrialization comprises the synthesis of cobalt carbonate and the lithium doping by sintering cobaltic; synthesizing cobalt hydroxide, and sintering to obtain the final product. The invention mainly adopts a synthetic route of a hydrogen-oxygen system in the cobalt oxyhydroxide, uses more lithium carbonate and is just combined with the subsequent composite coating.
CN 1039994711A discloses a preparation method of a doped and coated lithium cobaltate positive electrode material, which has the effects that anhydrous magnesium acetate, aluminum isopropoxide and tetraethoxysilane are dissolved in anhydrous ethanol, lithium cobaltate is mixed in a liquid phase, and Al, Mg and Si oxides are coated on the surface of the lithium cobaltate positive electrode material. The performance is also very good, and the industrialization is not easy to realize. CN 112909231A discloses a doped coated composite modified lithium cobaltate LCMO @ BT and a preparation method and application thereof, wherein a magnesium compound, a cobalt compound and a lithium salt are ball-milled and mixed uniformly; and pre-burning the mixture, then calcining at high temperature, and cooling to obtain the magnesium-doped lithium cobaltate. And calcining the mixture at high temperature, and cooling to obtain a product LCMO @ BT which can be used as an ultrahigh-pressure lithium cobaltate cathode material of a lithium ion battery. CN 110085810A discloses a preparation method and application of a coated modified lithium cobaltate positive electrode material, wherein a precursor of carbon-coated lithium vanadium phosphate is synthesized by a sol-gel method, then the precursor is sintered into carbon-coated lithium vanadium phosphate in a solid medium with oxygen isolation, then the prepared carbon-coated lithium vanadium phosphate is uniformly coated on the surface of a spherical lithium cobaltate substrate by dry coating, and finally the prepared carbon-coated lithium vanadium phosphate is sintered in the solid medium with oxygen isolation to obtain the coated modified lithium cobaltate positive electrode material. The invention is based on the difference of the processes that cobalt oxyhydroxide is selected as a precursor to prepare the small-particle single crystal. The composite modification is adopted to avoid the corrosion of electrolyte and side reaction, thereby realizing the extraction and the insertion of lithium under high voltage.
Disclosure of Invention
The invention aims to provide a preparation method of fluoride modified lithium cobaltate cathode material, which utilizes hydroxyl cobalt oxide and cobalt in hydroxide synthesis routeThe content is more than or equal to 68.5 percent. On the basis of the above-mentioned reaction, the water (H) formed between hydrofluoric acid (HF) and lithium hydroxy cobaltate2O) and lithium fluoride (LiF), LiF, which is insoluble in the electrolyte, inhibits the mobility of lithium ions at the electrode surface. HF reacts with lithium hexafluorophosphate (LiPF)6) Additional HF continues to be generated. Aluminum oxide coating and HF and H2AlF formed after O reaction3･H2O. can eliminate impurity H2O, thereby reducing the formation of HF. By compounding two reaction principles, the composite coating can promote the formation of a Co-Al-O-F substance, the substance can effectively inhibit the side reaction of electrolyte, and the surface impedance accumulation of the material under high voltage is reduced. The specific process is as follows:
a preparation method of a fluoride modified lithium cobaltate positive electrode material comprises the following specific steps:
a. sintered lithium cobaltate
Mixing cobalt oxyhydroxide and lithium carbonate in a certain ratio by a tank mill, roasting the mixture in a box-type atmosphere furnace at 1000 ℃, preserving the heat for 10 hours, and carrying out post-treatment on the sintered material to obtain small-particle single crystal lithium cobaltate;
b. preparation of the base Material
Mixing metal salt, LiCl and NH4F is completely dissolved in 500mL of deionized water and stirred for 2 h. Then 15g of lithium cobaltate was slowly added to the solution, heated at 25 ℃ and stirred for a further 2 h. And pouring the mixed solution into a PTFE high-pressure hydrothermal reaction kettle, and carrying out hydrothermal reaction for 5 hours in an air-blast drying oven at 180 ℃. Drying to obtain a base material;
c. sintering
And sintering the precursor C in a vacuum tube furnace in the atmosphere of argon gas at 550 ℃, preserving the temperature for 5 hours, and performing jaw crushing, roller pair crushing, airflow crushing and sieving on the sintered material to obtain the fluoride modified lithium cobaltate cathode material.
In the step a, the content of the product cobaltosic oxide in the cobalt oxyhydroxide is more than or equal to 68.5 percent.
In the step a, the ratio of the cobalt oxyhydroxide to the lithium carbonate is 1.04, and the air flow introduced into the box-type atmosphere furnace is 2.25m3H, the heating rate is 2 ℃/min.
Said step (c) isIn b, metal salt, LiCl and NH4The content of the modified material of F is 2.5 wt%, wherein the atomic mass ratio is 3: 1: and 5, washing the matrix material for three times, centrifuging by adopting hot water at the temperature of 85 ℃, and drying for 8 hours at the drying temperature of 95 ℃.
In the step b, the metal salt is Al salt, Ti salt, Mg salt, Zr salt or La salt.
In the step b, the metal salt is AlCl3·6H2And O. The use of hydrofluoric acid directly produces more HF, while the use of aluminum salts reduces HF production, which serves as a recombination reaction. One increase and one decrease to obtain composite double cladding of composite aluminum fluoride and fluoride. Because the cobalt chloride is adopted as the raw material and cobalt sulfate is not selected, the cobalt content of the reaction product is high, and the cobalt content of the sulfate radical reaction product is not higher than that of the chloride, the aluminum chloride is selected under the subsequent coating condition.
In the step c, powder prepressing is carried out at the pressure of 0.05MPa, and 3-5m of powder is introduced3The protective atmosphere of argon, the conditions of jaw breaking, roll pair and crushing, the air inlet pressure: 0.1-0.5 MPa; jaw breaking and double-roll crack spacing: 0.1-0.25 mm; jet milling frequency: 50-100 Hz; grading frequency: 10-150 Hz.
The invention utilizes the cobalt oxyhydroxide in the hydroxide synthesis route, and strictly selects the cobalt oxyhydroxide with the cobalt content of 68.5 percent as the characteristic of a precursor. On the basis, the surface of lithium cobaltate is compositely modified by an atomic deposition method. The specific innovation points are embodied in the following aspects:
(1) the sintering process is reduced: by using the characteristic that cobalt oxyhydroxide has high cobalt content and mixing with lithium carbonate to sinter the lithium cobaltate, the process of re-sintering the cobaltosic oxide is reduced, and the cost is greatly reduced.
(2) Two complex reaction principles are covered: one is that water (H) is formed between hydrofluoric acid (HF) and lithium hydroxy cobaltate2O) and lithium fluoride (LiF), LiF, which is insoluble in the electrolyte, inhibits the mobility of lithium ions at the electrode surface. HF reacts with lithium hexafluorophosphate (LiPF)6) Additional HF continues to be generated. The other is an alumina coating and HF and H2AlF formed after O reaction3･H2Can eliminateRemoving impurity H2O, thereby reducing the formation of HF.
(3) The fluoride modified lithium cobaltate cathode material has the electrochemical performance that the composite coating can promote the formation of Co-Al-O-F substances, and the substances can effectively inhibit the side reaction of electrolyte and reduce the material surface impedance accumulation under high voltage. Particularly, when the capacity is extremely decreased due to the occurrence of phase transition exceeding 4.35 v. Not only can maintain the stable structure through Al ions and inhibit phase change, but also can avoid the corrosion of the electrolyte through F ions.
Drawings
FIG. 1 is an SEM image of the preparation of layered cobalt oxyhydroxide;
FIG. 2 is an XRD pattern for the preparation of layered cobalt oxyhydroxide;
fig. 3 is an SEM image of a fluoride-modified lithium cobaltate positive electrode material prepared in example 1.
Detailed Description
Comparative example 1
Firstly, carrying out synthetic reaction on a mixed solution of 2mol/L cobalt chloride solution and 0.04mol/L EDTA and 8.0mol/L sodium hydroxide solution at the reaction synthetic temperature of 70 ℃, the stirring speed of 550 r/min and the air amount of 5m3The flow ratio is 5:1, the pH is controlled to be 11.0-12.5, and the material of the reaction kettle is titanium alloy. Two key factors are that the full kettle clean water is started and the ventilation volume needs to be injected for 2 hours in advance. By using a controlled crystallization method, the solid content in the kettle is observed to be about 35 percent, and the air quantity is large enough under the premise of high pH, so that the cobalt content (the main content of cobaltosic oxide is more than or equal to 90 percent) in the cobalt oxyhydroxide can be ensured to be 70.5 percent. And (3) performing ball milling on the dried cobalt oxyhydroxide and lithium carbonate by using a tank mill at the rotating speed of 250r/min, and uniformly mixing without obvious white spots. Roasting at 950 deg.c in oxygen-rich condition and maintaining for 15 hr. Powder post-treatment process: jaw crushing, roll crushing, crushing conditions, air inlet pressure: 0.1-3 MPa; jaw breaking and double-roll crack spacing: 0.1-0.3 mm; jet milling frequency: 50-100 Hz; grading frequency: 10-150 Hz to obtain the crushed and sintered monocrystal lithium cobaltate. According to the experimental scheme, the lithium-doped sintered monocrystal lithium cobaltate is directly doped, so that the process of sintering cobaltosic oxide is reduced, and the labor cost is greatly reduced. The experimental scheme is mainly thatUndoped pure-phase small-particle single-crystal layered lithium cobaltate.
Comparative example 2
Firstly, carrying out synthetic reaction on a mixed solution of 2mol/L cobalt chloride solution and 0.04mol/L EDTA and 8.0mol/L sodium hydroxide solution at the reaction synthetic temperature of 70 ℃, the stirring speed of 550 r/min and the air amount of 5m3The flow ratio is 5:1, the pH is controlled to be 11.0-12.5, and the material of the reaction kettle is titanium alloy. Two key factors are that the full kettle clean water is started and the ventilation volume needs to be injected for 2 hours in advance. By using a controlled crystallization method, the solid content in the kettle is observed to be about 35 percent, and the air quantity is large enough under the premise of high pH, so that the cobalt content (the main content of cobaltosic oxide is more than or equal to 90 percent) in the cobalt oxyhydroxide can be ensured to be 70.5 percent. And (3) performing ball milling on the dried cobalt oxyhydroxide and lithium carbonate by using a tank mill at the rotating speed of 250r/min, and uniformly mixing without obvious white spots. Roasting at 950 deg.c in oxygen-rich condition and maintaining for 15 hr. Powder post-treatment process: jaw crushing, roll crushing, crushing conditions, air inlet pressure: 0.1-3 MPa; jaw breaking and double-roll crack spacing: 0.1-0.3 mm; jet milling frequency: 50-100 Hz; grading frequency: 10-150 Hz to obtain the crushed and sintered monocrystal lithium cobaltate. Mixing single crystal lithium cobaltate with 2 wt% Al2O3Performing ball milling and mixing by a solid phase method, wherein the ball-material ratio is 1:10, the rotating speed is 500r/min, the time is 5h, and performing secondary sintering on the powder after ball milling is uniform by a planetary ball mill. Roasting at the low temperature of 550 ℃ for 8 hours to obtain the material, namely the aluminum-coated monocrystal lithium cobaltate material. The experimental scheme is that the nano-scale alumina powder is ball-milled and mixed by a solid phase method, and secondary sintering is carried out to coat aluminum.
Example 1
The precursor is cobaltosic oxide with the content of cobaltosic oxide in the cobalt oxyhydroxide being more than or equal to 68.5 percent. Mixing cobalt oxyhydroxide and 1.04 lithium carbonate in a ratio of 1:10, the ball milling time is 4h, and the rotating speed is 250 r/min. And roasting the sieved material through a box-type atmosphere furnace at 1000 ℃, preserving the heat for 10 hours, and carrying out post-treatment on the sintered material to obtain the small-particle single crystal lithium cobalt oxide. Mixing AlCl3·6H2O, LiCl and NH4The content of the modified material of F is 2.5% wt. in each case, wherein the atomic mass ratio isIs 3: 1: 5. according to stoichiometric ratio AlCl3·6H2O, LiCl and NH4F is completely dissolved in 500mL of deionized water and stirred for 2 h. Then 15g of lithium cobaltate was slowly added to the solution, heated at 25 ℃ and stirred for a further 2 h. And pouring the mixed solution into a PTFE high-pressure hydrothermal reaction kettle, and carrying out hydrothermal reaction for 5 hours in an air-blast drying oven at 180 ℃. Washing was carried out three times and centrifugation was carried out with hot water at 85 ℃. Drying at 95 deg.C for 8h to obtain matrix material. Pre-pressing the base material with 0.05MPa powder, introducing into a vacuum tube furnace for 3-5m3And h, sintering at 550 ℃ under the protection atmosphere of argon, preserving heat for 5h, and performing jaw crushing, roller pair, airflow crushing and sieving on the sintered material to obtain the fluoride modified lithium cobaltate cathode material. The solution is that the contents of the modified materials are all 2.5% by weight.
Example 2
The precursor is cobaltosic oxide with the content of cobaltosic oxide in the cobalt oxyhydroxide being more than or equal to 68.5 percent. Mixing cobalt oxyhydroxide and 1.04 lithium carbonate in a ratio of 1:10, the ball milling time is 4h, and the rotating speed is 250 r/min. And roasting the sieved material through a box-type atmosphere furnace at 1000 ℃, preserving the heat for 10 hours, and carrying out post-treatment on the sintered material to obtain the small-particle single crystal lithium cobalt oxide. Mixing AlCl3·6H2O, LiCl and NH4The content of the modified material of F is 1% wt., wherein the atomic mass ratio is 3: 1: 5. according to stoichiometric ratio AlCl3·6H2O, LiCl and NH4F is completely dissolved in 500mL of deionized water and stirred for 2 h. Then 15g of lithium cobaltate was slowly added to the solution, heated at 25 ℃ and stirred for a further 2 h. And pouring the mixed solution into a PTFE high-pressure hydrothermal reaction kettle, and carrying out hydrothermal reaction for 5 hours in an air-blast drying oven at 180 ℃. Washing was carried out three times and centrifugation was carried out with hot water at 85 ℃. Drying at 95 deg.C for 8h to obtain matrix material. Pre-pressing the base material with 0.05MPa powder, introducing into a vacuum tube furnace for 3-5m3And h, sintering at 550 ℃ under the protection atmosphere of argon, preserving heat for 5h, and performing jaw crushing, roller pair, airflow crushing and sieving on the sintered material to obtain the fluoride modified lithium cobaltate cathode material. This scheme is best compared to example 1The great difference is that the content of the modified material is 1% by weight.
Example 3
The precursor is cobaltosic oxide with the content of cobaltosic oxide in the cobalt oxyhydroxide being more than or equal to 68.5 percent. Mixing cobalt oxyhydroxide and 1.04 lithium carbonate in a ratio of 1:10, the ball milling time is 4h, and the rotating speed is 250 r/min. And roasting the sieved material through a box-type atmosphere furnace at 1000 ℃, preserving the heat for 10 hours, and carrying out post-treatment on the sintered material to obtain the small-particle single crystal lithium cobalt oxide. Mixing AlCl3·6H2O, LiCl and NH4The content of the modified material of F is 3.5% wt., wherein the atomic mass ratio is 3: 1: 5. according to stoichiometric ratio AlCl3·6H2O, LiCl and NH4F is completely dissolved in 500mL of deionized water and stirred for 2 h. Then 15g of lithium cobaltate was slowly added to the solution, heated at 25 ℃ and stirred for a further 2 h. And pouring the mixed solution into a PTFE high-pressure hydrothermal reaction kettle, and carrying out hydrothermal reaction for 5 hours in an air-blast drying oven at 180 ℃. Washing was carried out three times and centrifugation was carried out with hot water at 85 ℃. Drying at 95 deg.C for 8h to obtain matrix material. Pre-pressing the base material with 0.05MPa powder, introducing into a vacuum tube furnace for 3-5m3And h, sintering at 550 ℃ under the protection atmosphere of argon, preserving heat for 5h, and performing jaw crushing, roller pair, airflow crushing and sieving on the sintered material to obtain the fluoride modified lithium cobaltate cathode material. The embodiment differs from examples 1 and 2 to the greatest extent that the content of modifying material is 3.5% by weight.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (7)
1. A preparation method of a fluoride modified lithium cobaltate positive electrode material is characterized by comprising the following specific steps:
a. sintered lithium cobaltate
Mixing cobalt oxyhydroxide and lithium carbonate in a certain ratio by a tank mill, roasting the mixture in a box-type atmosphere furnace at 1000 ℃, preserving the heat for 10 hours, and carrying out post-treatment on the sintered material to obtain small-particle single crystal lithium cobaltate;
b. preparation of the base Material
Mixing metal salt, LiCl and NH4F is completely dissolved in 500mL of deionized water, stirred for 2h, then 15g of lithium cobaltate is slowly added into the solution, heated to 25 ℃, and continuously stirred for 2 h;
pouring the mixed solution into a PTFE high-pressure hydrothermal reaction kettle, carrying out hydrothermal reaction for 5 hours at 180 ℃ in a forced air drying oven, and drying to obtain a base material;
c. sintering
And sintering the precursor C in a vacuum tube furnace in the atmosphere of argon gas at 550 ℃, preserving the temperature for 5 hours, and performing jaw crushing, roller pair crushing, airflow crushing and sieving on the sintered material to obtain the fluoride modified lithium cobaltate cathode material.
2. The method for preparing the fluoride modified lithium cobaltate cathode material as claimed in claim 1, wherein in the step a, the content of cobaltosic oxide in the product of cobalt oxyhydroxide is not less than 68.5%.
3. The method for preparing the fluoride-modified lithium cobaltate cathode material as claimed in claim 1, wherein in the step a, the molar mass ratio of the cobalt oxyhydroxide to the lithium carbonate is 1.04, and the air flow rate introduced into the box-type atmosphere furnace is 2.25m3H, the heating rate is 2 ℃/min.
4. The method for preparing a fluoride-modified lithium cobaltate cathode material as claimed in claim 1, wherein in the step b, metal salt, LiCl and NH are added4The content of the modified material of F is 2.5 wt%, wherein the atomic mass ratio is 3: 1: and 5, washing the matrix material for three times, centrifuging by adopting hot water at the temperature of 85 ℃, and drying for 8 hours at the drying temperature of 95 ℃.
5. The method for preparing the fluoride-modified lithium cobaltate cathode material as claimed in claim 1, wherein in the step b, the metal salt is Al salt, Ti salt, Mg salt, Zr salt or La salt.
6. The method for preparing the fluoride modified lithium cobaltate cathode material as claimed in claim 5, wherein in the step b, the metal salt is AlCl3·6H2O。
7. The method for preparing the fluoride modified lithium cobaltate cathode material as claimed in claim 1, wherein in the step c, powder prepressing is required, the pressure is 0.05MPa, and 3-5m is introduced3The protective atmosphere of argon, the conditions of jaw breaking, roll pair and crushing, the air inlet pressure: 0.1-0.5 MPa; jaw breaking and double-roll crack spacing: 0.1-0.25 mm; jet milling frequency: 50-100 Hz; grading frequency: 10-150 Hz.
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| CN115432742A (en) * | 2022-09-09 | 2022-12-06 | 浙江格派钴业新材料有限公司 | Preparation method of composite precursor material |
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