CN110980817A - High-power and long-cycle lithium battery positive electrode material and preparation method thereof - Google Patents
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Abstract
The invention is applicable to the field of lithium battery anode material manufacturing, and provides a high-power and long-cycle lithium battery anode material and a preparation method thereof, the invention adopts a two-step method to prepare the lithium battery anode material, firstly takes modified MOF as a template, synthesizing a high-power nickel-cobalt-manganese oxide precursor by regulating and controlling the feeding speed of a metal solution, ammonia water (with a low ammonia value) and sodium hydroxide and controlling the pH and solid content of a reaction solution, then sintering, crushing, washing, drying and coating are carried out to prepare the anode material meeting the requirement, the interior of the anode material is of a porous structure, has a relatively high specific surface area and small particle size, the contact area of the electrolyte ensures that the electrolyte fully infiltrates the anode material, provides effective support for high-current high-rate charge and discharge, and simultaneously improves the cycle performance and the service life of the anode material.
Description
Technical Field
The invention belongs to the field of lithium battery anode material manufacturing, and particularly relates to a high-power and long-cycle lithium battery anode material and a preparation method thereof.
Background
A lithium ion battery is a secondary battery (rechargeable battery) that mainly operates by movement of lithium ions between a positive electrode and a negative electrode. During charging and discharging, Li+Intercalation and deintercalation to and from two electrodes: when charged, Li+The lithium ion battery is extracted from the positive electrode and is inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true when discharging, and the battery generally adopts a material containing lithium as an electrode, which is representative of modern high-performance batteries.
Different from other rechargeable batteries, the lithium ion battery has the capacity which slowly declines along with the increase of the use times in the charging and discharging processes, and the electrode is easy to release and insert excessive lithium ions in the charging process, so that the crystal lattice collapse is caused, and the Li is reduced+Conductivity, resulting in increased impedance, internal consumption, and reduced rate performance of the battery, thereby shortening the service life.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a high power and long cycle lithium battery positive electrode material and a preparation method thereof, and aims to solve the technical problems of low conductivity, low rate capability and short service life of the conventional lithium battery positive electrode material.
In one aspect, the method for preparing the high power and long cycle lithium battery cathode material comprises the following steps:
step S1, preparing MOFs material by taking sodium metaaluminate, terephthalic acid and sodium hydroxide as reaction raw materials;
s2, weighing a nickel source, a cobalt source and a manganese source according to a certain metal molar ratio to prepare a mixed solution A; adding a certain amount of emulsifier and the MOFs material obtained in the step S1 into a sodium hydroxide solution serving as a base solution, and uniformly stirring to obtain a mixed solution B; preparing a low-concentration ammonia water solution C; introducing A, B, C three solutions into a reaction kettle according to the reaction molar ratio at different flow rates, controlling the pH of the solutions, carrying out solid-liquid separation after reacting for a period of time to obtain a precipitate, and washing, drying and calcining the obtained precipitate at high temperature to obtain the nickel-cobalt-manganese oxide;
and S3, uniformly mixing the nickel-cobalt-manganese oxide obtained in the step S2 and a lithium source according to a certain proportion, sintering, crushing, washing with water, drying, uniformly mixing the dried product and boric acid powder, and coating by a dry method to obtain the high-power and long-cycle lithium battery cathode material.
Specifically, in step S2, the metal molar ratio is nNi：nCo：nMnThe ratio of the nickel source to the cobalt source to the manganese source is 80:10:10, the corresponding sulfate or nitrate is used as the nickel source, the corresponding cobalt source and the corresponding manganese source, the concentration of the sodium hydroxide solution is 4.0mol/L, the concentration of the ammonia water solution is 0.2-0.4 mol/L, the emulsifier is hexadecyl trimethyl ammonium bromide, the flow rate of the mixed solution A is 2-3L/h, the flow rate of the mixed solution B is 2-3L/h, and the flow rate of the ammonia water solution C is 8-10L/h.
Specifically, in step S2, the temperature in the reaction kettle is 40-80 ℃, the pH value of the solution is stabilized at 11.0-12.8, the reaction time is 15-40h, and nitrogen is introduced for protection in the reaction process.
Specifically, in step S3, sintering is performed in a pure oxygen atmosphere furnace at 800 ℃ for 10-12 hours.
Specifically, in step S1, the reaction raw materials are stirred at room temperature for 1 hour, uniformly mixed, and then heated by microwave at 120 ℃ for reaction for 2 hours to obtain a suspension, and the suspension is precipitated, washed with deionized water for several times, and dried to obtain the MOFs material.
On the other hand, the invention also provides a high-power and long-cycle lithium battery cathode material, which is prepared by adopting the method.
The invention has the beneficial effects that: the invention adopts a two-step method to prepare the lithium battery anode material, firstly takes modified MOF as a template, synthesizes a high-power nickel-cobalt-manganese oxide precursor by regulating the feeding speed of a metal solution, ammonia water (with a low ammonia value) and sodium hydroxide and controlling the pH and solid content of a reaction solution, and then prepares the anode material meeting the requirement by sintering, crushing, washing, drying and coating treatment.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In this embodiment, the preparation method of the high-power and long-cycle lithium battery positive electrode material includes the following steps:
and step S1, preparing the MOFs material by taking sodium metaaluminate, terephthalic acid and sodium hydroxide as reaction raw materials.
In the step, sodium metaaluminate, terephthalic acid and sodium hydroxide are mixed and then stirred for 1h at room temperature, after the sodium metaaluminate, the terephthalic acid and the sodium hydroxide are uniformly mixed, the mixture is heated and reacted for 2h at 120 ℃ by using microwaves to obtain turbid liquid, the turbid liquid is subjected to solid-liquid separation to obtain precipitates, then the obtained precipitates are washed for a plurality of times by using deionized water and dried to obtain the MOFs material with uniform size and 2-4 microns of particle size.
S2, weighing a nickel source, a cobalt source and a manganese source according to a certain metal molar ratio to prepare a mixed solution A; adding a certain amount of emulsifier and the MOFs material obtained in the step S1 into a sodium hydroxide solution serving as a base solution, and uniformly stirring to obtain a mixed solution B; preparing a low-concentration ammonia water solution C; and then introducing A, B, C three solutions into a reaction kettle according to the reaction molar ratio at different flow rates, controlling the pH of the solutions, carrying out solid-liquid separation after reacting for a period of time to obtain a precipitate, and washing, drying and calcining the obtained precipitate at high temperature to obtain the nickel-cobalt-manganese oxide.
In this step, the metal molar ratio is nNi：nCo：nMnThe ratio of nickel to manganese to the total amount of nickel is 80:10:10, corresponding sulfate or nitrate is used as the nickel source, the cobalt source and the manganese source, the concentration of the sodium hydroxide solution is 4.0mol/L, the concentration of the ammonia water solution is 0.2-0.3 mol/L, the emulsifier is cetyl trimethyl ammonium bromide, the flow rate of the mixed solution A is 2-3L/h, the flow rate of the mixed solution B is 2-3L/h, the flow rate of the ammonia water solution C is 8-10L/h, the temperature in the reaction kettle is 40-80 ℃, the pH value of the solution is stabilized at 11.0-12.8, the reaction time is 15-40h, and nitrogen is introduced for protection in the reaction process.
In the step, the concentration of the ammonia water solution needs to be strictly controlled, and the low ammonia value is a key step for preparing the needle-shaped whisker precursor, so that the concentration of the ammonia water solution is selected to be 0.2-0.4 mol/L.
In the step, cetyl trimethyl ammonium bromide is used as an emulsifier, so that the MOFs material can be uniformly dispersed in the sodium hydroxide solution, and conditions are created for preparing the anode material with uniform particle size.
In the high-temperature calcination process, aluminum in the MOFs material can further penetrate into the interior of the precursor to play a role in stabilizing the lattice structure, and a foundation is laid for preparing a high-power and long-cycle lithium battery anode material.
And S3, uniformly mixing the nickel-cobalt-manganese oxide obtained in the step S2 and a lithium source according to a certain proportion, sintering, crushing, washing with water, drying, uniformly mixing the dried product and boric acid powder, and coating by a dry method to obtain the high-power and long-cycle lithium battery cathode material.
The step is carried out in a pure oxygen atmosphere furnace, the sintering temperature is 800 ℃, the sintering time is 10-12 h, and the subsequent dry coating in the step is carried out by adopting the conventional process in the field, which is not described again.
In order to explain the technical means of the present invention, the following description will be given by way of specific examples.
The first embodiment is as follows:
1. mixing sodium metaaluminate, terephthalic acid and sodium hydroxide, stirring for 1h at room temperature, heating and reacting for 2h at 120 ℃ by using microwaves after the sodium metaaluminate, the terephthalic acid and the sodium hydroxide are uniformly mixed to obtain turbid liquid, carrying out solid-liquid separation on the turbid liquid to obtain a precipitate, washing the precipitate for a plurality of times by using deionized water, and drying to obtain the MOFs material with uniform size and 2-4 microns of particle size.
2. According to the metal molar ratio nNi：nCo：nMnWeighing NiSO4 & 6H at 80:10:102O、CoSO4·7H2O and MnSO 4. H2O, preparing a mixed solution A with the total molar concentration of metal ions of 2.0 mol/L; preparing 4.0mol/L sodium hydroxide solution, then adding emulsifying agents of cetyl trimethyl ammonium bromide and MOFs, and uniformly stirring to obtain mixed solution B; preparing 0.4mol/L ammonia water solution C, then leading the mixed solution A into a 50 ℃ reaction kettle at a flow rate of 2.5L/h, the mixed solution B at a flow rate of 2.5L/h and the ammonia water solution C at a flow rate of 10L/h, controlling the flow rate of the sodium hydroxide solution to maintain the pH of the whole reaction system at 11-12.5, continuing to react for 25h after the pH of the reaction system is stable, and obtaining Ni after the reaction is finished through solid-liquid separation, washing and drying0.80Co0.10Mn0.10(OH)2Calcining the powder at the high temperature of 550 ℃ to obtain a nickel-cobalt-manganese oxide with loose and porous interior;
3. weighing 3.10kgNi0.80Co0.10Mn0.10O2Powder and 1.88kg of LiOH. H2O, after being uniformly stirred and mixed in a high-speed stirrer, putting the mixture into an oxygen atmosphere furnace for calcining at the calcining temperature of 800 ℃ for 20 hours, after the reaction is finished, cooling, crushing and sieving to obtain an NCM positive electrode material matrix, and washing and drying the NCM positive electrode material matrix for later use;
4. weighing 1.8kg of standby NCM positive electrode material matrix and 15.4g of boric acid, uniformly mixing in a mixer at a high speed, and preserving heat for 10 hours at 270 ℃ to obtain the positive electrode material with the surface of the nickel cobalt lithium manganate positive electrode material matrix coated with a layer of boron oxide.
Example two:
1. mixing sodium metaaluminate, terephthalic acid and sodium hydroxide, stirring for 1h at room temperature, heating and reacting for 2h at 120 ℃ by using microwaves after the sodium metaaluminate, the terephthalic acid and the sodium hydroxide are uniformly mixed to obtain turbid liquid, carrying out solid-liquid separation on the turbid liquid to obtain a precipitate, washing the precipitate for a plurality of times by using deionized water, and drying to obtain the MOFs material with uniform size and 2-4 microns of particle size.
2. According to the metal molar ratio nNi：nCo：nMnWeighing NiSO4 & 6H at 80:10:102O、CoSO4·7H2O and MnSO 4. H2O, preparing a mixed solution A with the total molar concentration of metal ions of 2.0 mol/L; preparing 4.0mol/L sodium hydroxide solution, then adding emulsifying agents of cetyl trimethyl ammonium bromide and MOFs, and uniformly stirring to obtain mixed solution B; preparing 0.4mol/L ammonia water solution C, then leading the mixed solution A into a reaction kettle with the temperature of 55 ℃ at the flow rate of 2.5L/h, leading the mixed solution B into a reaction kettle with the flow rate of 2.5L/h, leading the ammonia water solution C into the reaction kettle with the flow rate of 10L/h, controlling the flow rate of the sodium hydroxide solution to maintain the pH of the whole reaction system at 11.8-12.0, continuing to react for 25h after the pH of the reaction system is stable, and obtaining Ni after the reaction is finished through solid-liquid separation, washing and drying0.80Co0.10Mn0.10(OH)2Calcining the powder at the high temperature of 550 ℃ to obtain a nickel-cobalt-manganese oxide with loose and porous interior;
3. weighing 3.10kgNi0.80Co0.10Mn0.10O2Powder and 1.88kg of LiOH. H2O, after being uniformly stirred and mixed in a high-speed stirrer, putting the mixture into an oxygen atmosphere furnace for calcining at the calcining temperature of 750 ℃ for 24 hours, cooling, crushing and sieving after the reaction is finished to obtain an NCM positive electrode material matrix, and washing and drying the NCM positive electrode material matrix for later use;
4. weighing 1.8kg of standby NCM positive electrode material matrix and 15.4g of boric acid, uniformly mixing in a mixer at a high speed, and preserving heat for 10 hours at 270 ℃ to obtain the positive electrode material with the surface of the nickel cobalt lithium manganate positive electrode material matrix coated with a layer of boron oxide.
Comparative example one:
1. according to the metal molar ratio nNi：nCo：nMnWeighing NiSO4 & 6H at 80:10:102O、CoSO4·7H2O and MnSO 4. H2O, preparing a mixed solution A with the total molar concentration of metal ions of 2.0 mol/L; preparing 4.0mol/L sodium hydroxide solution B; preparing 0.4mol/L ammonia water solution C, then leading the mixed solution A at the flow rate of 2.5L/h, the mixed solution B at the flow rate of 2.5L/h, leading the ammonia water solution C at the flow rate of 10L/h into a reaction kettle at the temperature of 50 ℃, controlling the flow rate of a sodium hydroxide solution to maintain the pH of the whole reaction system at 11.5-12.5, continuing to react for 25h after the pH of the reaction system is stable, and obtaining Ni after the reaction is finished through solid-liquid separation, washing and drying0.80Co0.10Mn0.10(OH)2Calcining the powder at the high temperature of 550 ℃ to obtain nickel-cobalt-manganese oxide;
2. weighing 3.10kgNi0.80Co0.10Mn0.10O2Powder and 1.88kg of LiOH. H2O, after being uniformly stirred and mixed in a high-speed stirrer, putting the mixture into an oxygen atmosphere furnace for calcining at the calcining temperature of 800 ℃ for 20 hours, after the reaction is finished, cooling, crushing and sieving to obtain an NCM positive electrode material matrix, and washing and drying the NCM positive electrode material matrix for later use;
3. weighing 1.8kg of standby NCM positive electrode material matrix and 15.4g of boric acid, uniformly mixing in a mixer at a high speed, and preserving heat for 10 hours at 270 ℃ to obtain the positive electrode material with the surface of the nickel cobalt lithium manganate positive electrode material matrix coated with a layer of boron oxide.
Comparative example two:
1. according to the metal molar ratio nNi：nCo：nMnWeighing NiSO4 & 6H at 80:10:102O、CoSO4·7H2O and MnSO 4. H2O, configured as metal ionsThe total concentration of the mols is 2.0 mol/L; preparing 4.0mol/L sodium hydroxide solution B; preparing 0.4mol/L ammonia water solution C, then enabling the mixed solution A to flow at a flow rate of 2.5L/h, the mixed solution B to flow at a flow rate of 2.5L/h, enabling the ammonia water solution C to flow into a reaction kettle at 55 ℃ at a flow rate of 10L/h, controlling the flow rate of a sodium hydroxide solution to enable the pH of the whole reaction system to be maintained at 11.8-12.0, continuing to react for 25h after the pH of the reaction system is stable, and obtaining Ni after the reaction is finished through solid-liquid separation, washing and drying0.80Co0.10Mn0.10(OH)2Calcining the powder at the high temperature of 550 ℃ to obtain nickel-cobalt-manganese oxide;
2. weighing 3.10kgNi0.80Co0.10Mn0.10O2Powder and 1.88kg of LiOH. H2O, after being uniformly stirred and mixed in a high-speed stirrer, putting the mixture into an oxygen atmosphere furnace for calcining at the calcining temperature of 750 ℃ for 24 hours, cooling, crushing and sieving after the reaction is finished to obtain an NCM positive electrode material matrix, and washing and drying the NCM positive electrode material matrix for later use;
3. weighing 1.8kg of standby NCM positive electrode material matrix and 15.4g of boric acid, uniformly mixing in a mixer at a high speed, and preserving heat for 10 hours at 270 ℃ to obtain the positive electrode material with the surface of the nickel cobalt lithium manganate positive electrode material matrix coated with a layer of boron oxide.
The positive electrode materials prepared in the first embodiment, the second embodiment, the first comparative embodiment and the second comparative embodiment are respectively mixed with acetylene black serving as a conductive agent and PVDF serving as a binder according to a mass ratio of 80: 12: 8, adding a proper amount of 1-methyl-2 pyrrolidone, ball milling for 1 hour to prepare slurry, uniformly coating the slurry on an aluminum sheet, drying and tabletting to prepare the positive plate. The 2032 button cell is assembled by using a metal lithium sheet as a cathode, and an electrical performance test (the charging and discharging voltage is 2.75-4.3V) is carried out by adopting a Siken test system.
The final test results for the two examples and comparative examples are shown in the following table:
as can be seen from the above table, the lithium battery prepared by using the cathode material coated by the two-step method has significant advantages in the first effect percentage and the cycle retention rate of 50 times compared with the lithium battery prepared by directly using the cathode material coated by boron.
The invention adopts a two-step method to prepare the lithium battery anode material, firstly takes modified MOF as a template, synthesizes a high-power nickel-cobalt-manganese oxide precursor by regulating the feeding speed of a metal solution, ammonia water (with a low ammonia value) and sodium hydroxide and controlling the pH and solid content of a reaction solution, and then prepares the anode material meeting the requirement by sintering, crushing, washing, drying and coating treatment.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. A preparation method of a high-power and long-cycle lithium battery positive electrode material is characterized by comprising the following steps:
step S1, preparing MOFs material by taking sodium metaaluminate, terephthalic acid and sodium hydroxide as reaction raw materials;
s2, weighing a nickel source, a cobalt source and a manganese source according to a certain metal molar ratio to prepare a mixed solution A; adding a certain amount of emulsifier and the MOFs material obtained in the step S1 into a sodium hydroxide solution serving as a base solution, and uniformly stirring to obtain a mixed solution B; preparing a low-concentration ammonia water solution C; introducing A, B, C three solutions into a reaction kettle at different flow rates according to the reaction molar ratio, controlling the pH of the solutions, reacting for a period of time, carrying out solid-liquid separation to obtain a precipitate, and washing, drying and calcining the obtained precipitate at high temperature to obtain the nickel-cobalt-manganese oxide;
and S3, uniformly mixing the nickel-cobalt-manganese oxide obtained in the step S2 and a lithium source according to a certain proportion, sintering, crushing, washing with water, drying, uniformly mixing the dried product and boric acid powder, and coating by a dry method to obtain the high-power and long-cycle lithium battery cathode material.
2. The method for preparing a high power and long cycle positive electrode material for lithium batteries according to claim 1, wherein the metal molar ratio is n in step S2Ni：nCo：nMnThe ratio of the nickel source to the cobalt source to the manganese source is 80:10:10, the corresponding sulfate or nitrate is used as the nickel source, the corresponding cobalt source and the corresponding manganese source, the concentration of the sodium hydroxide solution is 4.0mol/L, the concentration of the ammonia water solution is 0.2-0.4 mol/L, the emulsifier is cetyl trimethyl ammonium bromide, the flow rate of the mixed solution A is 2-3L/h, the flow rate of the mixed solution B is 2-3L/h, and the flow rate of the ammonia water solution C is 8-10L/h.
3. The method for preparing a high-power and long-cycle lithium battery positive electrode material as claimed in claim 1, wherein in step S2, the temperature in the reaction vessel is 40-80 ℃, the pH of the solution is stabilized at 11.0-12.8, the reaction time is 15-40h, and nitrogen is introduced for protection during the reaction process.
4. The method for preparing a high power and long cycle positive electrode material for a lithium battery as claimed in claim 1, wherein the sintering is performed in a pure oxygen atmosphere furnace at a sintering temperature of 800 ℃ for 10-12 hours in step S3.
5. The method for preparing a high-power and long-cycle lithium battery positive electrode material as claimed in claim 1, wherein in step S1, the reaction raw materials are mixed and stirred for 1h at room temperature, and after being uniformly mixed, the reaction raw materials are heated and reacted for 2h at 120 ℃ by using microwaves to obtain a suspension, and after the suspension is precipitated, the suspension is washed with deionized water for several times and then dried to obtain the MOFs material.
6. A high power and long cycle positive electrode material for lithium batteries, characterized in that it is prepared by the method according to any one of claims 1 to 5.
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| CN111498915A (en) * | 2020-04-26 | 2020-08-07 | 株洲升华科技有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN112125352A (en) * | 2020-08-20 | 2020-12-25 | 天津巴莫科技有限责任公司 | Preparation method of high-nickel cathode material |
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| CN111498915A (en) * | 2020-04-26 | 2020-08-07 | 株洲升华科技有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN112125352A (en) * | 2020-08-20 | 2020-12-25 | 天津巴莫科技有限责任公司 | Preparation method of high-nickel cathode material |
| CN112125352B (en) * | 2020-08-20 | 2022-12-30 | 天津巴莫科技有限责任公司 | Preparation method of high-nickel cathode material |
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