CN115986077A - Positive electrode lithium supplement material and preparation method and application thereof - Google Patents
Positive electrode lithium supplement material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a positive electrode lithium supplement material and a preparation method and application thereof. The positive electrode lithium supplement material comprises a matrix, a secondary coating layer coated on the surface of the matrix and an outermost carbon coating layer, wherein the matrix comprises lithium iron oxide containing doping elements; the doping element comprises any one or combination of at least two of cerium, ruthenium, antimony, zirconium, iridium or niobium; the coating element in the secondary coating layer comprises any one or the combination of at least two of silicon, tantalum, magnesium or strontium. According to the invention, the doping and coating of the material are realized simultaneously by adopting the specific doping element and the coating element, and the carbon coating layer is arranged on the surface of the outermost layer, so that the residual alkali content of the material is reduced, the conductivity of the material is improved, and when the carbon coating layer is used for a battery, the first charge capacity of the battery is improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a positive electrode lithium supplement material and a preparation method and application thereof.
Background
Nowadays, research on lithium ion batteries has been greatly advanced, and specific capacity, cycling stability, rate capability and the like are all improved, but there are many problems. Among these, irreversible capacity loss, which is mostly due to lithium ions consumed in forming a solid electrolyte membrane during the first charge, limits the application of many energetic materials.
In the first charging process of a lithium ion battery, after an organic solvent (such as diethyl carbonate (DEC), dimethyl carbonate (DMC), propylene Carbonate (PC) and the like) in an electrolyte abstracts lithium ions from a positive electrode, the organic solvent is easily reduced and decomposed on the surface of a negative electrode, and then a passivation film, called a solid electrolyte phase interface film, i.e., an SEI film, is generated. The SEI film can insulate electrons from passing through to allow lithium ions to pass through, is an electronic insulator, but is an excellent ion conductor, and can effectively inhibit further decomposition of the electrolyte, thereby preventing the formation of a thicker SEI film after the first cycle. The SEI film mainly contains organic components such as RCOOLi, ROLi and ROCO2Li, and Li 2 CO 3 、Li 2 Inorganic components such as O, liOH and LiF. The process of forming these lithium-containing components is irreversible and thus permanently consumes a portion of the Li from the positive electrode + Reducing the first cycle coulombic efficiency (ICE) and resulting in lower energy and capacity densities for lithium ion batteries.
Therefore, researchers have developed lithium supplement techniques to add new lithium sources to electrode materials by way of lithium supplement to compensate for the loss of active lithium caused by SEI film formation in the first cycle. The positive pole lithium supplement is that the lithium supplement material is added as an additive in the positive pole homogenizing process, when the battery core is prepared and charged for the first time, the positive pole lithium supplement material has higher gram capacity and lower first effect, a large amount of lithium ions are separated in the normal charging process and are used for supplementing the lithium ions consumed by the SEI film formed by the negative pole, and a large amount of lithium ions cannot be accepted due to the lower first effect in the discharging process, so that the capacity of the battery is improved. The existing positive electrode lithium supplement additive has a high residual alkali value, the residual alkali can react with positive electrode binder polyvinylidene fluoride (PVDF), chemical gel is easy to generate in the stirring process of slurry, the viscosity of the slurry is improved, and the processing of a pole piece is influenced. In addition, these residual alkalis may react with the electrolyte at high temperatures to generate carbon dioxide or other solid substances, which may increase the gas generation rate of the battery or increase the battery impedance, and eventually cause a decrease in the battery performance.
CN107863567A uses conductive metal doped Li2O powder to make positive electrode lithium-supplementing material, which can supplement lithium and further improve battery capacity, but in actual use, because Li 2 The reaction of trace amounts of water in O (which reacts with water to produce LiOH, a strong base) and N-methylpyrrolidone (NMP) tends to cause decomposition and deactivation of PVDF, leading to coagulation of the positive electrode slurry, failure to coat, and, secondly, li of the insulator even if coated in a very harsh, anhydrous environment 2 O can lead to incomplete decomposition in the process of first charging and lithium supplementing, and gas can still be generated in the using process of the battery, so that the safety problem caused by the expansion and the rupture of the battery is caused.
Therefore, how to reduce the residual alkali in the positive electrode lithium-supplementing material and improve the conductivity of the material is a technical problem to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a positive electrode lithium supplement material, and a preparation method and application thereof. According to the invention, the doping and coating of the material are realized simultaneously by adopting the specific doping elements and the specific coating elements, and the carbon coating layer is arranged on the surface of the outermost layer, so that the residual alkali content of the material is reduced, the conductivity of the material is improved, and the first charge capacity of the battery is improved when the carbon coating material is used for the battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a positive electrode lithium supplement material, which comprises a substrate, a secondary coating layer coated on the surface of the substrate and an outermost carbon coating layer, wherein the substrate comprises a lithium iron oxide containing a doping element; the doping element comprises any one or combination of at least two of cerium, ruthenium, antimony, zirconium, iridium or niobium; the coating element in the secondary coating layer comprises any one or the combination of at least two of silicon, tantalum, magnesium or strontium.
According to the invention, specific doping elements and coating elements are adopted, the doping elements and the coating elements in the coating layer have a synergistic effect, the element types can not be changed, and meanwhile, the carbon coating layer on the outermost layer is matched, so that the residual alkali content of the material is reduced, the conductivity of the material is improved, and when the carbon coating layer is used for a battery, the first charge capacity of the battery is improved.
Preferably, the powder compaction densities F, D10 and D90 of the positive electrode lithium supplement material satisfy the following conditions: 1.0 ≦ F/(D10 × D90). Ltoreq.1.5, where the compacted density F is the compacted density at a pressure of 2t, for example 1, 1.1, 1.2, 1.3, 1.4 or 1.5, etc.
According to the invention, a relational expression among powder compacted densities F, D10 and D90 of the positive electrode lithium supplement material is established, and parameter results are regulated and controlled simultaneously, so that the slurry viscosity regulation during homogenization is facilitated, and the subsequent processing is facilitated, if the relational expression is less than 1, the particle size is small, the powder compaction is low, the viscosity regulation during the homogenization is not facilitated, and the coating cannot be performed due to large viscosity rebound; if the particle size is larger than 1.5, the particle size is larger, and the powder compaction is correspondingly higher, so that the battery capacity is lower, and the use requirement cannot be met.
In a second aspect, the present invention provides a method for preparing a positive electrode lithium supplement material according to the first aspect, the method comprising the steps of:
(1) Mixing a lithium source, an iron source and a doping agent, and sintering to obtain a base material;
(2) Mixing a base material and a coating agent for the first time, sintering for the first time, mixing a product obtained after the first sintering with a carbon source for the second time, and sintering for the second time to obtain the anode lithium supplement material;
wherein the dopant comprises any one of or a combination of at least two of a cerium source, a ruthenium source, an antimony source, a zirconium source, an iridium source or a niobium source; the coating element in the coating agent comprises any one of a silicon source, a tantalum source, a magnesium source or a strontium source or a combination of at least two of the silicon source, the tantalum source, the magnesium source and the strontium source.
The preparation method provided by the invention is simple and feasible, the doping agent is directly added in the preparation process of the matrix material, the bulk phase doping of the doping element is realized, then the cladding of the cladding agent is carried out, and finally the cladding of the carbon layer is carried out, so that the positive electrode lithium supplement material with low residual alkali and good conductivity is obtained.
In the present invention, the raw materials of the lithium source, the iron source and the carbon source are not particularly limited, and the raw materials of the cerium source, the ruthenium source, the antimony source, the zirconium source, the iridium source and the niobium source in the dopant, and the raw materials of the silicon source, the tantalum source and the magnesium source in the coating agent are not particularly limited, and the raw materials can be used for sintering and can be used for reaction, and the present invention is applicable to, for example:
lithium sources conventional in the art such as lithium hydroxide monohydrate, lithium hydroxide anhydrous, lithium chloride, lithium bromide, lithium carbonate, and the like.
Iron sources conventional in the art such as ferric oxide, ferric chloride, ferric nitrate, ferric sulfate, ferric bromide, and the like.
Zirconium sources conventional in the art, such as zirconia, zirconium sulfide, zirconium bicarbonate, zirconium silicate, zirconium boride, zirconium tungstate, zirconium dichromate, zirconium hydroxide, zirconium nitrate, zirconium phosphate, or zirconium chloride, and the like.
Cerium sources conventional in the art, such as cerium oxide, cerium carbonate, cerium sulfate, cerium phosphate, and the like.
Ruthenium sources conventional in the art, such as ruthenium acetate, ammonium chlororuthenate, ruthenium trichloride, ruthenium oxide, ruthenium iodide, potassium chlororuthenate, and the like.
Niobium sources conventional in the art such as niobium pentoxide, lithium niobate, niobium ethoxide, niobium pentafluoride, niobium pentachloride, and the like.
Antimony sources conventional in the art, such as antimony trioxide, halogenated (F/Cl/Br) antimony, triphenylantimony, and the like.
Sources of iridium conventional in the art, e.g.Iridium sesquioxide, iridium dioxide, iridium hydroxide, iridium sulfide, iridium chloride, and iridium hexachloro-diamino ((NH) 4 ) 2 IrCl 6 ) Etc. can be used in the present invention.
Silicon sources conventional in the art, such as silicon dioxide, silicic acid, silicon fluoride or silicon chloride, and the like.
Tantalum sources conventional in the art such as tantalum pentoxide, tantalum pentachloride, tantalum nitride, tantalic acid, potassium fluorotantalate, or tantalum sulfide, and the like.
Magnesium sources conventional in the art, such as magnesium oxalate, magnesium acetate, magnesium oxide, magnesium carbonate or magnesium hydroxide.
Strontium sources conventional in the art such as strontium oxalate, strontium acetate, strontium oxide, strontium carbonate, strontium nitrate or strontium titanate, and the like.
Carbon sources conventional in the art, such as polyethylene glycol, polypropylene, phenolic resin, epoxy resin, polyimide, polycarbonate, glucose, or the like.
Preferably, in step (1), the mass ratio of the doping element in the dopant, iron in the iron source, and lithium in the lithium source is (0.0005-0.01): 1 (5-6), for example, 0.0005.
Preferably, the mixing of step (1) comprises liquid phase mixing.
According to the invention, through liquid phase mixing, raw materials can be well mixed uniformly, and a material with uniform components is obtained.
Preferably, the liquid phases are dynamically dried after mixing.
In the invention, dynamic drying is more beneficial to material drying, and the hardening phenomenon caused by static drying is avoided, thereby reducing the post-treatment of the process.
Preferably, the temperature of the dynamic drying is 100 to 150 ℃, such as 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃.
Preferably, the dynamic drying pressure is-0.04 to-0.2 MPa, such as-0.04 MPa, -0.05MPa, -0.1MPa, -0.13MPa, -0.15MPa, -0.18MPa or-0.2 MPa.
Preferably, the dynamic drying time is 1 to 10h, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, etc.
Preferably, the sintering temperature in step (1) is 600-900 ℃, such as 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃, etc.
Preferably, the sintering time in step (1) is 10-20 h, such as 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h.
Preferably, the addition amount N of the dopant, the addition amount M of the coating agent and the total alkali content Ex-Li of the positive electrode lithium supplement material satisfy 2 ≦ Ex-Li/(N + M) ≦ 50, such as 2, 3, 5, 8, 10, 12, 13, 15, 18, 20, 23, 24, 25, 28, 30, 33, 35, 36, 38, 40, 43, 45, 48 or 50, and the like.
In the invention, the regulation and control of the residual alkali amount of the lithium-supplementing material of the positive electrode are realized by regulating and controlling the addition amounts of the doping agent and the coating agent, and when the addition amount is not within the range of 2-50 and is not within the range of 2-50, the purpose of reducing the residual alkali cannot be realized, and meanwhile, the relation between the residual alkali amount and the addition amounts of the doping agent and the coating agent cannot be accurately reflected by regulating the relational expression.
Preferably, the mass ratio of the coating agent to the base material is (0.0005 to 0.01): 1, for example, 0.0005.
Preferably, the rotation speed of the primary mixing in the step (2) is 100-300 rpm, such as 100rpm, 150rpm, 200rpm, 250rpm or 300 rpm.
Preferably, the time for the first mixing in step (2) is 1 to 5 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours and the like.
Preferably, the time for the primary sintering in the step (2) is 2 to 10 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours.
Preferably, the temperature of the primary sintering in step (2) is 500 to 700 ℃, such as 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃ or the like.
Preferably, in the step (2), the mass ratio of the product after primary sintering to the carbon source is 1 (2-10), for example, 1.
Preferably, the temperature of the secondary sintering in the step (2) is 200 to 300 ℃, such as 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃ or 300 ℃ and the like.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) Mixing a lithium source, an iron source and a dopant in a mass ratio of doping elements in the dopant to iron in the iron source to lithium in the lithium source of (0.0005-0.01): 1- (5-6) in a liquid phase, dynamically drying at 100-150 ℃ and-0.04-0.2 Mpa for 1-10 h, and sintering at 600-900 ℃ for 10-20 h to obtain a matrix material;
(2) Carrying out primary mixing on a base material and a coating agent for 1-5 h at 100-300 rpm according to the mass ratio of 1 (0.0005-0.01), carrying out primary sintering at 500-700 ℃, carrying out secondary mixing on a product obtained after the primary sintering and a carbon source according to the mass ratio of the product obtained after the primary sintering to the carbon source of 1 (1-10), and carrying out secondary sintering at 200-300 ℃ to obtain the positive electrode lithium supplement material;
wherein the dopant comprises any one of or a combination of at least two of a cerium source, a ruthenium source, an antimony source, a zirconium source, an iridium source or a niobium source; the coating element in the coating agent comprises any one or the combination of at least two of a silicon source, a tantalum source, a magnesium source or a strontium source; the addition amount N of the doping agent, the addition amount M of the coating agent and the total alkali content Ex-Li of the positive electrode lithium supplement material meet the condition that Ex-Li/(N + M) is less than or equal to 2 and less than or equal to 50.
In a third aspect, the present invention further provides a lithium ion battery, which includes the positive electrode lithium supplement material according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, specific doping elements and coating elements are adopted, the doping elements and the coating elements in the coating layer have a synergistic effect, the element types can not be changed, and meanwhile, the carbon coating layer on the outermost layer is matched, so that the residual alkali content of the material is reduced, the conductivity of the material is improved, when the carbon coating layer is used for a battery, the first charge capacity of the battery is improved, the preparation method is simple, and the carbon coating layer is suitable for large-scale production. The positive electrode lithium supplement material provided by the invention is added into the positive electrode of the battery, and the powder compaction densities F, D10 and D90 of the positive electrode lithium supplement material meet the following requirements: F/(D10 × D90) is more than or equal to 1.0 and less than or equal to 1.5, and when the addition amount N of the doping agent, the addition amount M of the coating agent and the total alkali content Ex-Li of the positive electrode lithium supplement material in the preparation process of the positive electrode lithium supplement material meet 2 or more than or equal to Ex-Li/(N + M) and less than or equal to 50, compared with a control group (the positive electrode lithium supplement material in the invention is not added in the positive electrode), the charge capacity at 0.1C can be improved by more than 9.06 percent.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The present embodiment provides a positive electrode lithium supplement material, which includes a substrate, a secondary coating layer coated on the surface of the substrate, and an outermost carbon coating layer, wherein the substrate includes a lithium iron oxide (undoped chemical formula is Li) containing cerium as a doping element 5 FeO 4 ) (ii) a The coating element in the secondary coating layer is tantalum.
The preparation method of the anode lithium supplement material comprises the following steps:
(2) Adding cerium oxide, ferric chloride and lithium hydroxide into 1.5L of organic solvent ethanol according to the mass ratio of 0.002;
(2) Weighing tantalum pentoxide and a base material according to a mass ratio of 0.0035 to 1.0, putting the tantalum pentoxide and the base material into a planetary ball mill for mixing (mixing conditions: rotating speed 200rpm, mixing time 3 h), putting the mixture into a high-temperature atmosphere furnace, and sintering for 6h at 600 ℃ under the protection of argon atmosphere to obtain a primary sintered product;
(3) And (3) uniformly mixing the primary sintered product and polyethylene glycol (the mass ratio of the primary sintered product to the polyethylene glycol is 1.
Examples 2 to 5
In examples 2 to 5, the amounts of the dopant and the capping agent added were adjusted so that F/(D10 × D90) (powder compaction densities F, D10, and D90) and Ex-Li/(N + M) (the amount of the dopant added N, the amount of the capping agent added M, and the total alkali content of the positive electrode lithium-supplementing material Ex-Li) of the materials were different.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 1
The comparative example differs from example 1 in that the comparative example does not include Li 5 FeO 4 Doping and cladding are carried out.
The remaining preparation methods and parameters were in accordance with example 1.
The F/(D10 × D90) and Ex-Li/(N + M) as well as the total alkali content of the materials in examples 1 to 5 and comparative example 1 are shown in table 1.
TABLE 1
| F/(D10*D90) | Ex-Li/(N+M) | Total alkali content (ppm) | |
| Example 1 | 1.1 | 12 | 25500 |
| Example 2 | 1.2 | 24 | 18400 |
| Example 3 | 1.3 | 36 | 13720 |
| Example 4 | 1.5 | 50 | 20500 |
| Example 5 | 2 | 60 | 40080 |
| Comparative example 1 | 0.5 | - | 41300 |
Preparing the positive electrode lithium supplement materials provided in the embodiments 1 to 5 and the comparative example 1 to obtain button cells, respectively weighing the positive electrode lithium supplement materials, the lithium iron phosphate positive electrode material, SP, PVDF glue solution and NMP, homogenizing, coating and baking, drying the pole pieces, and performing rolling, cutting and 2032 button cell assembly, wherein the lithium iron phosphate positive electrode material: SP: PVDF powder =90 (mass ratio), and the positive electrode lithium supplement material accounts for 2% of the lithium iron phosphate positive electrode material. The electrochemical performance results are after being applied to the positive electrode material (the positive electrode lithium supplement material is not added in the control group).
The test conditions were: the results of the first cycle charge and discharge test at 0.1C at 3 to 4.3V are shown in table 2.
TABLE 2
The data results in table 1 and table 2 show that:
from the data results of examples 1 to 5, it is understood that the positive electrode lithium-replenishing material having 1.0. Ltoreq. F/(D10. Multidot. D90). Ltoreq.1.5 and 2. Ltoreq. Ex-Li/(N + M). Ltoreq.50 has a better lithium-replenishing effect, and if the particle size of the material is outside the above range, the particle size becomes too large or too small, the powder compaction becomes too large or too small, and the homogenizing effect, the slurry viscosity, and the lithium-replenishing effect are impaired. After carbon coating, the air stability and the conductivity of the lithium supplement material are greatly improved.
From the data results of examples 1 to 4 and comparative example 1, it can be seen that the positive electrode lithium supplement material provided by the present invention has lower residual alkali and higher first cycle charge capacity than the pure lithium supplement material without doping and coating.
In summary, the invention adopts specific doping elements and coating elements, the doping elements and the coating elements in the coating layer have synergistic action, the element types can not be changed, and the outermost carbon coating layer is matched, so that the residual alkali content of the material is reduced, the conductivity of the material is improved, when the material is used for a battery, the first charge capacity of the battery is improved, the preparation method is simple, and the material is suitable for large-scale production. The positive electrode lithium supplement material provided by the invention is added into the positive electrode of the battery, and the powder compaction densities F, D10 and D90 of the positive electrode lithium supplement material meet the following requirements: F/(D10 × D90) is more than or equal to 1.0 and less than or equal to 1.5, and when the addition amount N of the doping agent, the addition amount M of the coating agent and the total alkali content Ex-Li of the positive electrode lithium supplement material in the preparation process of the positive electrode lithium supplement material meet 2 or more than or equal to Ex-Li/(N + M) and less than or equal to 50, compared with a control group (the positive electrode lithium supplement material in the invention is not added in the positive electrode), the charge capacity at 0.1C can be improved by more than 9.06 percent.
The applicant states that the present invention is illustrated by the above embodiments, but the present invention is not limited to the above embodiments, that is, the present invention does not mean that the present invention must be implemented by the above embodiments. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The positive electrode lithium supplement material is characterized by comprising a substrate, a secondary coating layer coated on the surface of the substrate and an outermost carbon coating layer, wherein the substrate comprises a lithium iron oxide containing doping elements; the doping element comprises any one or combination of at least two of cerium, ruthenium, antimony, zirconium, iridium or niobium; the coating element in the secondary coating layer comprises any one or the combination of at least two of silicon, tantalum, magnesium or strontium.
2. The positive electrode lithium supplement material according to claim 1, wherein the powder compaction densities F, D10 and D90 of the positive electrode lithium supplement material satisfy the following conditions: 1.0 ≤ F/(D10 × D90) ≤ 1.5, wherein the compacted density F is a compacted density under a pressure of 2 t.
3. A method for preparing a positive electrode lithium supplement material according to claim 1 or 2, comprising the steps of:
(1) Mixing a lithium source, an iron source and a doping agent, and sintering to obtain a base material;
(2) Mixing a base material and a coating agent for the first time, sintering for the first time, mixing a product obtained after the sintering for the first time and a carbon source for the second time, and sintering for the second time to obtain the anode lithium supplement material;
wherein the dopant comprises any one of or a combination of at least two of a cerium source, a ruthenium source, an antimony source, a zirconium source, an iridium source or a niobium source; the coating element in the coating agent comprises any one or the combination of at least two of a silicon source, a tantalum source, a magnesium source or a strontium source.
4. The method for preparing a lithium supplement material for a positive electrode according to claim 3, wherein in the step (1), the mass ratio of the doping element in the dopant, iron in the iron source and lithium in the lithium source is (0.0005-0.01): 1 (5-6);
preferably, the mixing of step (1) comprises liquid phase mixing;
preferably, the liquid phases are dynamically dried after being mixed;
preferably, the temperature of the dynamic drying is 100-150 ℃;
preferably, the pressure of the dynamic drying is-0.04 to-0.2 MPa;
preferably, the dynamic drying time is 1 to 10 hours.
5. The method for preparing the positive electrode lithium supplement material according to claim 3 or 4, wherein the sintering temperature in the step (1) is 600-900 ℃;
preferably, the sintering time in the step (1) is 10-20 h.
6. The method for preparing a positive electrode lithium supplement material according to any one of claims 3 to 5, wherein 2. Ltoreq. Ex-Li/(N + M). Ltoreq.50 is satisfied between the addition amount N of the dopant, the addition amount M of the coating agent, and the total alkali content Ex-Li of the positive electrode lithium supplement material.
7. The method for producing a positive electrode lithium supplement material according to any one of claims 3 to 6, wherein in the step (2), the mass ratio of the coating agent to the base material is (0.0005 to 0.01): 1;
preferably, the rotation speed of the primary mixing in the step (2) is 100-300 rpm;
preferably, the time for the primary mixing in the step (2) is 1-5 h;
preferably, the time of the primary sintering in the step (2) is 2-10 h;
preferably, the temperature of the primary sintering in the step (2) is 500-700 ℃.
8. The method for preparing the positive electrode lithium supplement material according to any one of claims 3 to 7, wherein in the step (2), the mass ratio of the product after primary sintering to the carbon source is 1 (2-10);
preferably, the temperature of the secondary sintering in the step (2) is 200-300 ℃.
9. The method for preparing the positive electrode lithium supplement material according to any one of claims 3 to 8, wherein the method comprises the following steps:
(1) Mixing a lithium source, an iron source and a dopant in a mass ratio of doping elements in the dopant to iron in the iron source to lithium in the lithium source of (0.0005-0.01): 1- (5-6) in a liquid phase, dynamically drying at 100-150 ℃ and-0.04-0.2 Mpa for 1-10 h, and sintering at 600-900 ℃ for 10-20 h to obtain a matrix material;
(2) Carrying out primary mixing on a base material and a coating agent for 1-5 h at 100-300 rpm according to the mass ratio of 1 (0.0005-0.01), carrying out primary sintering at 500-700 ℃, carrying out secondary mixing on a product obtained after the primary sintering and a carbon source according to the mass ratio of the product obtained after the primary sintering to the carbon source being 1 (2-10), and carrying out secondary sintering at 200-300 ℃ to obtain the cathode lithium supplement material;
wherein the dopant comprises any one of or a combination of at least two of a cerium source, a ruthenium source, an antimony source, a zirconium source, an iridium source or a niobium source; the coating element in the coating agent comprises any one or the combination of at least two of a silicon source, a tantalum source, a magnesium source or a strontium source; the addition amount N of the doping agent, the addition amount M of the coating agent and the total alkali content Ex-Li of the positive electrode lithium supplement material meet the condition that Ex-Li/(N + M) is less than or equal to 2 and less than or equal to 50.
10. A lithium ion battery, characterized in that it comprises a positive electrode lithium supplement material according to claim 1 or 2.
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| CN117219777A (en) * | 2023-11-07 | 2023-12-12 | 江苏正力新能电池技术有限公司 | Lithium supplementing agent, preparation method thereof, positive electrode plate and secondary battery |
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2022
- 2022-12-27 CN CN202211691077.9A patent/CN115986077A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117219777A (en) * | 2023-11-07 | 2023-12-12 | 江苏正力新能电池技术有限公司 | Lithium supplementing agent, preparation method thereof, positive electrode plate and secondary battery |
| CN117219777B (en) * | 2023-11-07 | 2024-03-15 | 江苏正力新能电池技术有限公司 | Lithium supplementing agent, preparation method thereof, positive electrode plate and secondary battery |
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