CN111933926A - Lithium ion battery anode material precursor and preparation method thereof - Google Patents
Lithium ion battery anode material precursor and preparation method thereof Download PDFInfo
- Publication number
- CN111933926A CN111933926A CN202010800024.0A CN202010800024A CN111933926A CN 111933926 A CN111933926 A CN 111933926A CN 202010800024 A CN202010800024 A CN 202010800024A CN 111933926 A CN111933926 A CN 111933926A
- Authority
- CN
- China
- Prior art keywords
- soluble
- salt
- lithium ion
- ion battery
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a precursor of a lithium ion battery anode material and a preparation method thereof, belonging to the technical field of battery materials. The precursor of the lithium ion battery material is a nickel-cobalt-manganese-magnesium-titanium high-entropy oxide, a high-nickel-cobalt-manganese oxide and a nickel-cobalt-manganese-magnesium-titanium high-entropy oxide in sequence from an outer layer to an inner layer. The battery material takes the high-entropy material as the crystal nucleus and the surface coating, effectively solves the safety problem of the high-nickel ternary material, improves the stability and the cyclicity of the battery material, has higher charge-discharge gram capacity, and reaches the middle-grade level in the industry. The technical scheme has the advantages of simple preparation process and low production cost, and is suitable for industrialization.
Description
Technical Field
The invention belongs to the field of high-entropy battery materials, and particularly relates to a precursor of a lithium ion battery positive electrode material and a preparation method thereof.
Background
The lithium ion battery has the characteristics of high working voltage, high energy density, long cycle life, small self-discharge rate, low pollution, no memory effect and the like, and is a research and application hotspot of the current energy industry. The ternary lithium nickel cobalt manganese oxide cathode material is gradually favored by the market due to the advantages of high energy density, good cycle performance, stable working voltage, simple preparation process and the like, and the market share is continuously increased. Particularly in the field of power batteries, the lithium battery positive electrode material is considered to be the most promising new lithium battery positive electrode material at present, and has been successfully applied to the field of electric vehicles, such as Tesla in the united states, honda in japan, biedi in china, jianhuai, and the like.
The high-entropy material is a novel multi-principal-element material consisting of multiple elements in an equimolar ratio or a nearly equimolar ratio, and breaks through the traditional material design concept. Different from the traditional material, the multi-principal-element high-entropy material has complex components, and the atoms of the constituent elements are randomly and disorderly distributed on lattice positions, so that the high-entropy material has a high-entropy effect in thermodynamics, a slow diffusion effect in kinetics, a lattice distortion effect in structure and a cocktail effect in performance. Under the coupling action of various strengthening mechanisms, the high-entropy material has excellent characteristics which cannot be compared with a plurality of traditional materials.
For example, chinese publication No. CN110600703A discloses a five-membered transition metal oxide high-entropy material for lithium ion batteries, which is prepared by using equimolar metal nitrate, then adding glycine, ethylene diamine tetraacetic acid, hexamethylenetetramine, hexamethylenediisocyanate, citric acid or oxalic acid, and performing high-temperature heat preservation to obtain a five-membered spinel type oxide high-entropy material with a chemical formula of (Cr)0.2Fe0.2Mn0.2Zn0.2M0.2)3O4Wherein M is a divalent metal cation Co2+Or Ni2+。
By analyzing the content of the above patent, it can be found that the high-entropy material still cannot meet the safe use requirement of the lithium ion battery.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems, the invention provides a preparation method of a lithium ion battery anode material precursor, which effectively solves the problems of safety and cyclicity of a high nickel-cobalt-manganese material and has higher charge and discharge capacity.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the lithium ion battery material precursor is sequentially aNi from the outer layer to the inner layer0.2Co0.2Mn0.2Mg0.2Ti0.2O1.2-bNixCoyMnzO-cNi0.2Co0.2Mn0.2Mg0.2 Ti0.2O1.2(ii) a Wherein: x + y + z is 1, and x is more than or equal to 0.6; a + b + c is 1, b: (a + c) 7-9: 1-3, c: a is 4-20: 1.
the preparation method of the lithium ion battery anode material precursor comprises the following steps:
(1) preparing transparent solutions of battery-grade soluble nickel salt, soluble cobalt salt and soluble manganese salt in a beaker a according to a certain proportion, and preparing transparent solutions of soluble nickel salt, soluble cobalt salt, soluble manganese salt, soluble magnesium salt and soluble titanium salt in equimolar quantities in a beaker b;
(2) adding the solution b in a beaker, ammonia water and alkali liquor into a reactor, stirring and reacting, controlling the pH value of the reaction to be unchanged, stopping feeding after 5-25% of the solution b in the beaker is added, adding glutamic acid and introducing N2Continuously stirring for half an hour;
(3) adding the solution of the beaker a, ammonia water and alkali liquor into the reactor in the step (2), and continuously introducing N2Controlling the reaction pH notChanging until the beaker a is added completely, and continuing stirring for 1-3 h; generating a high-nickel ternary material on the basis of the high-entropy quinary material;
(4) and adding the residual solution in the beaker b, ammonia water and alkali liquor into the reactor, controlling the reaction pH to be unchanged, stirring and aging for 1-4 h after the materials are added, washing, drying and dehydrating to obtain the product.
In one possible embodiment of the present invention, the transparent solution of soluble nickel salt, soluble cobalt salt and soluble manganese salt in step (1) is prepared by dissolving nickel salt in a beaker a: the molar ratio of the soluble cobalt salt to the soluble manganese salt is 6-9: 4-1;
the total molar concentration of the three salts in the beaker a is 1-6 mol/L; preferably 2-4 mol/L;
total molar amount of three salts in said beaker a: the total molar amount of the five salts in the beaker b is 7-9: 3-1;
the total molar concentration of the five salts in the beaker b is 1-6 mol/L; preferably 2-4 mol/L;
the soluble nickel salt, the soluble cobalt salt, the soluble manganese salt and the soluble magnesium salt are all battery-grade sulfates or nitrates with the valence of +2 corresponding to each other, and the soluble titanium salt is titanyl sulfate or titanium nitrate.
In one possible embodiment of the present invention, the pH in the step (2) is 11.0 to 12.5; preferably 11.5 to 12.0;
the addition amount of the glutamic acid is 1-5% of the addition molar amount of soluble nickel salt, soluble cobalt salt and soluble manganese salt; preferably 2 to 3 percent.
In one possible embodiment of the present invention, N is the same as in step (2) and step (3)2The feeding speed is the same, namely the volume of gas fed in every minute is 0.4-2 reactor volumes.
In one possible embodiment of the invention, the concentration of the ammonia water in the step (2), the step (3) and the step (4) is 1-6 mol/L; preferably 2-4 mol/L; the total molar weight of the ammonia water is 0.2-0.8 times of the total molar weight of the salt; preferably 0.4 to 0.6 times;
the alkali liquor is at least one of sodium hydroxide, sodium carbonate and sodium bicarbonate, and the concentration of the alkali liquor is 2-10 mol/L; preferably 4 to 6 mol/L.
In one possible embodiment of the present invention, the reaction temperature in step (2) and step (3) and step (4) is the same, and is 40 to 90 ℃, preferably 50 to 65 ℃.
In one possible embodiment of the present invention, the method according to claim 1, wherein the pH in the step (3) is 10.5 to 11.5.
In one possible embodiment of the present invention, the pH in the step (4) is 10.5 to 11.5; the drying temperature is 100 ℃; the dehydration temperature is 600-1000 ℃.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
1) the lithium ion battery material precursor prepared by the invention is sequentially nickel-cobalt-manganese-magnesium-titanium high-entropy oxide, high-nickel-cobalt-manganese oxide, nickel-cobalt-manganese-magnesium-titanium high-entropy oxide from the outer layer to the inner layer, the technical scheme creatively takes the nickel-cobalt-manganese-magnesium-titanium high-entropy oxide as a crystal nucleus, the nickel-cobalt-manganese oxide grows on the crystal nucleus, and the nickel-cobalt-manganese-titanium high-entropy oxide is coated on the outer layer, so that the safety and the cyclicity of the high-nickel-cobalt-manganese material can be effectively solved, and the charging and discharging capacity is higher; the material cost is low, the production process is simple, and the large-scale production is facilitated;
2) the invention relates to a ternary nickel-cobalt-manganese-magnesium-titanium high-entropy lithium manganese battery which takes nickel-cobalt-manganese-magnesium-titanium high-entropy oxide as a crystal nucleus, grows nickel-cobalt-manganese oxide on the crystal nucleus and is coated with the nickel-cobalt-manganese-magnesium-titanium high-entropy oxide on the outer layer. Can effectively solve the problems of safety and cyclicity of the high nickel-cobalt-manganese material, and has higher charge and discharge capacity.
Detailed Description
Exemplary embodiments of the present invention are described in detail below. Although these exemplary embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, it should be understood that other embodiments may be realized and that various changes to the invention may be made without departing from the spirit and scope of the present invention. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. Accordingly, the scope of the invention is to be limited only by the following claims.
The experimental procedures used in the following examples are conventional unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The preparation method of the precursor of the lithium ion battery anode material comprises the following steps:
(1) preparing transparent solutions of battery-grade soluble nickel salt, soluble cobalt salt and soluble manganese salt in a beaker a according to a certain proportion, and preparing transparent solutions of soluble nickel salt, soluble cobalt salt, soluble manganese salt, soluble magnesium salt and soluble titanium salt in equimolar quantities in a beaker b; and (3) dissolving the transparent solution of soluble nickel salt, soluble cobalt salt and soluble manganese salt in a beaker a: the molar ratio of the soluble cobalt salt to the soluble manganese salt is 6-9: 4-1; the total molar concentration of the three salts in the beaker a is 1-6 mol/L; preferably 2-4 mol/L; total molar amount of three salts in said beaker a: the total molar amount of the five salts in the beaker b is 7-9: 3 to 1.
(2) Adding the solution b in a beaker, ammonia water and alkali liquor into a reactor, stirring and reacting, controlling the pH value of the reaction to be unchanged, stopping feeding after 5-25% of the solution b in the beaker is added, adding glutamic acid and introducing N2Continuously stirring for half an hour; the total molar concentration of the five salts in the beaker b is 1-6 mol/L; preferably 2-4 mol/L; the soluble nickel salt, the soluble cobalt salt, the soluble manganese salt and the soluble magnesium salt are all battery-grade sulfates or nitrates with the valence of +2 corresponding to each other, and the soluble titanium salt is titanyl sulfate or titanium nitrate.
(3) Adding the solution of the beaker a, ammonia water and alkali liquor into the reactor in the step (2), and continuously introducing N2Controlling the reaction pH to be unchanged until the beaker a is added, and continuously stirring for 1-3 h; high nickel ternary material is generated on the basis of high entropy quinary material(ii) a The pH is 11.0-12.5; preferably 11.5 to 12.0; the addition amount of the glutamic acid is 1-5% of the addition molar amount of soluble nickel salt, soluble cobalt salt and soluble manganese salt; preferably 2 to 3 percent.
(4) And adding the residual solution in the beaker b, ammonia water and alkali liquor into the reactor, controlling the reaction pH to be unchanged, stirring and aging for 1-4 h after the materials are added, washing, drying and dehydrating to obtain the product. The pH is 10.5-11.5; the drying temperature is 100 ℃; the dehydration temperature is 600-1000 ℃.
Example 1
(1) Respectively weighing 6mol of nickel sulfate, 2mol of cobalt sulfate and 2mol of manganese sulfate transparent solution in a beaker a, wherein the total volume is 10L, and then respectively weighing 0.85mol of nickel sulfate, 0.85mol of cobalt sulfate, 0.85mol of manganese sulfate, 0.85mol of magnesium sulfate and 0.85mol of titanyl sulfate transparent solution in a beaker b, wherein the volume is 4.25L;
(2) adding the solution b in a beaker, 2.85L of 1mol/L ammonia water and 10mol/L sodium hydroxide solution into a 30L reactor, stirring for reaction, controlling the reaction pH to be 12.5 at 40 ℃, adding 5 percent of the solution b in the beaker, stopping adding the solution b, adding 14.7g of glutamic acid, introducing N2Continuously stirring for half an hour with the flow rate of 12L/min;
(3) adding the solution of the beaker a, 1mol/L ammonia water and 10mol/L sodium hydroxide solution into the reactor in the step (2), and continuously introducing N2Controlling the reaction pH to be 10.5 unchanged at the flow rate of 12L/min until the beaker a is added completely, and continuing stirring for 1 h;
(4) and (3) adding the residual solution in the beaker b, 1mol/L ammonia water and 10mol/L sodium hydroxide solution into the reactor, controlling the reaction pH to be 10.5, stirring and aging for 4 hours after the materials are added, washing, drying at 100 ℃, and dehydrating at 1000 ℃ to obtain the product.
Example 2
(1) Respectively weighing 7mol of nickel sulfate, 2mol of cobalt sulfate and 1mol of manganese sulfate transparent solution in a beaker a, wherein the total volume is 2L, and then respectively weighing 0.5mol of nickel sulfate, 0.5mol of cobalt sulfate, 0.5mol of manganese sulfate, 0.5mol of magnesium sulfate and 0.5mol of titanyl sulfate transparent solution in a beaker b, wherein the volume is 0.5L;
(2) beaker b solution, 5mol/L ammonia water 2.0L, 2mAdding ol/L sodium carbonate solution into a 30L reactor, stirring for reaction at 90 deg.C, controlling reaction pH to 11.0, adding 10% of solution in beaker b, stopping adding, adding 73.5g glutamic acid, and introducing N2Continuously stirring for half an hour with the flow rate of 30L/min;
(3) adding the solution of the beaker a, 5mol/L ammonia water and 2mol/L sodium carbonate solution into the reactor in the step (2), and continuously introducing N2Controlling the reaction pH to be 11.5 unchanged at the flow rate of 30L/min until the beaker a is added completely, and continuing stirring for 2 hours;
(4) and adding the residual solution in the beaker b, 5mol/L ammonia water and 2mol/L sodium carbonate solution into the reactor, controlling the reaction pH to be 11.5, stirring and aging for 1h after the materials are added, washing, drying at 100 ℃, and dehydrating at 600 ℃ to obtain the product.
Example 3
1) Respectively weighing 8.5mol of nickel nitrate, 1mol of cobalt nitrate and 0.5mol of manganese nitrate transparent solution in a beaker a, wherein the total volume is 4L, and then respectively weighing 0.22mol of nickel nitrate, 0.22mol of cobalt nitrate, 0.22mol of manganese nitrate, 0.22mol of magnesium nitrate and 0.22mol of titanium nitrate transparent solution in a beaker b, wherein the volume is 0.44L;
(2) adding the solution b in a beaker, 1.83L of 3mol/L ammonia water and 6mol/L of sodium hydroxide solution into a 30L reactor, stirring for reaction, controlling the reaction pH to be 11.5 at 55 ℃, stopping adding after 10% of the solution b in the beaker is added, adding 36.75g of glutamic acid, introducing N2Continuously stirring for half an hour with the flow rate of 60L/min;
(3) adding the solution of the beaker a, 3mol/L ammonia water and 6mol/L sodium hydroxide solution into the reactor in the step (2), and continuously introducing N2Controlling the reaction pH to be 11.0 unchanged at a flow rate of 60L/min until the beaker a is added, and continuing stirring for 3 hours;
(4) and adding the residual solution in the beaker b, 3mol/L ammonia water and 6mol/L sodium hydroxide solution into the reactor, controlling the reaction pH to be 11.0, stirring and aging for 2h after the materials are added, washing, drying at 100 ℃, and dehydrating at 800 ℃ to obtain the product.
Example 4
1) Respectively weighing 7mol of nickel nitrate, 1.5mol of cobalt nitrate and 1.5mol of manganese nitrate transparent solution in a beaker a, wherein the total volume is 5L, and then respectively weighing 0.4mol of nickel nitrate, 0.4mol of cobalt nitrate, 0.4mol of manganese nitrate, 0.4mol of magnesium nitrate and 0.4mol of titanium nitrate transparent solution in a beaker b, wherein the volume is 1.0L;
(2) adding the solution b in a beaker, 2.0L of 3mol/L ammonia water and 5mol/L of sodium hydroxide solution into a 30L reactor, stirring for reaction, controlling the reaction pH to be 12.0 at 55 ℃, stopping adding after 10% of the solution b in the beaker is added, adding 36.75g of glutamic acid, introducing N2Continuously stirring for half an hour with the flow rate of 40L/min;
(3) adding the solution of the beaker a, 3mol/L ammonia water and 5mol/L sodium hydroxide solution into the reactor in the step (2), and continuously introducing N2Controlling the reaction pH to be 10.5 unchanged at the flow rate of 40L/min until the beaker a is added completely, and continuing stirring for 2 hours;
(4) and adding the residual solution in the beaker b, 3mol/L ammonia water and 5mol/L sodium hydroxide solution into the reactor, controlling the reaction pH to be 10.5, stirring and aging for 2h after the materials are added, washing, drying at 100 ℃, and dehydrating at 1000 ℃ to obtain the product.
Comparative example 1
(1) Respectively weighing 6mol of nickel sulfate, 2mol of cobalt sulfate and 2mol of manganese sulfate transparent solution in a beaker a, wherein the total volume is 10L;
(2) adding the beaker solution a, 2.0L of 1mol/L ammonia water and 10mol/L sodium hydroxide solution into a 30L reactor, stirring for reaction at the reaction temperature of 40 ℃, controlling the reaction pH to be 10.5, adding 14.7g of glutamic acid, introducing N2And the flow is 12L/min until the beaker a is added completely, the stirring is continued for 4 hours, and the product is obtained by washing, drying at 100 ℃ and then dehydrating at 1000 ℃.
Comparative example 2
(1) Weighing 0.85mol of nickel sulfate, 0.85mol of cobalt sulfate, 0.85mol of manganese sulfate, 0.85mol of magnesium sulfate and 0.85mol of transparent titanyl sulfate solution in a beaker b, wherein the volume of the transparent solution is 4.25L;
(2) adding the solution b in a beaker, 0.85L of 1mol/L ammonia water and 10mol/L sodium hydroxide solution into a 30L reactor, stirring for reaction at the reaction temperature of 40 ℃, controlling the reaction pH to be 10.5, adding 14.7g of glutamic acid, introducing N2The flow rate is 12L/min,and (4) continuing stirring for 4 hours until the beaker b is added completely, washing, drying at 100 ℃, and dehydrating at 1000 ℃ to obtain the product.
Comparative example 3
The conditions were the same except that ammonia was not added in steps (2), (3) and (4) in example 1.
Comparative example 4
The conditions were the same except that nitrogen was not introduced in steps (2) and (3) in example 1.
The gram discharge capacity after addition of lithium carbonate for the examples and comparative examples is shown in Table 1 below.
TABLE 1 gram Capacity after lithium carbonate discharge
The data in table 1 show that the high-entropy oxide has good cycle performance, and the cycle stability of the lithium ion battery can be effectively improved by adopting the structure of nickel-cobalt-manganese-titanium high-entropy oxide-high-nickel-cobalt-manganese-titanium high-entropy oxide-nickel-cobalt-manganese-magnesium-titanium high-entropy oxide.
The method comprises the following steps that (2), step (3) and step (4) are matched, firstly, in the step (2), high-entropy quinary materials are mainly used as crystal nuclei, the reaction pH is high, particles are small, nitrogen is introduced to provide nitrogen protection for generating high-nickel ternary materials after the reaction is finished, sodium glutamate generated by the reaction of glutamic acid and alkali plays a role, the appearance of the surface of the generated crystal nuclei is controlled, the rugged surface can be obtained, meanwhile, the materials in the step (3) can conveniently grow on the surface of the crystal nuclei, and the high-nickel ternary materials are generated on the basis of the high-entropy quinary materials; in the step (4), the high-nickel ternary material can be synthesized, and then the surface of the high-entropy ternary material is wrapped with the high-entropy quinary material, so that the obtained high-entropy material has good stability, the cycle stability and the safety performance are improved, and the pH is lower than that in the step (2) and small particles are not needed. The three steps are not necessary, the sequence cannot be reversed, the steps are connected in order, the obtained lithium ion battery material precursor is sequentially nickel-cobalt-manganese-magnesium-titanium high-entropy oxide-high-nickel-cobalt-manganese-oxide-nickel-cobalt-manganese-magnesium-titanium high-entropy oxide from the outer layer to the inner layer, the high-entropy material can effectively solve the safety and the cyclicity of the high-nickel-cobalt-manganese material, and the charge-discharge capacity is high.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and it should be noted that, for those skilled in the art, several modifications or equivalent substitutions can be made without departing from the principle of the present invention, and the spirit and scope of the technical solutions should be covered by the claims of the present invention.
Claims (10)
1. The precursor of the lithium ion battery anode material is characterized by sequentially comprising aNi from an outer layer to an inner layer0.2Co0.2Mn0.2Mg0.2Ti0.2O1.2-bNixCoyMnzO-cNi0.2Co0.2Mn0.2Mg0.2Ti0.2O1.2(ii) a Wherein: x + y + z is 1, and x is more than or equal to 0.6; a + b + c is 1, b: (a + c) 7-9: 1-3, c: a is 4-20: 1.
2. the preparation method of the precursor of the lithium ion battery positive electrode material according to claim 1, characterized by comprising the following steps:
(1) preparing a soluble nickel salt, a soluble cobalt salt and a soluble manganese salt transparent solution in a container a according to a certain proportion, and preparing an equimolar amount of soluble nickel salt, soluble cobalt salt, soluble manganese salt, soluble magnesium salt and soluble titanium salt transparent solution in a container b;
(2) adding the solution in the container b, ammonia water and alkali liquor into a reactor, stirring for reaction, controlling the pH value of the reaction to be constant, adding the solution in the container b by 5-25%, stopping feeding, adding glutamic acid and introducing N2Continuously stirring for half an hour;
(3) adding the solution in the container a, ammonia water and alkali liquor into the reactor in the step (2), and continuously introducing N2Controlling the pH value of the reaction to be unchanged until the container a is added, and continuing stirring for 1-3 h;
(4) and (4) adding the residual solution in the container b, ammonia water and alkali liquor into the reactor, controlling the reaction pH to be unchanged, stirring and aging for 1-4 h after the materials are added, washing, drying and dehydrating to obtain the product.
3. The method for preparing a precursor of a positive electrode material of a lithium ion battery according to claim 2, wherein the transparent solution of the soluble nickel salt, the soluble cobalt salt and the soluble manganese salt in the step (1) is placed in a container a, wherein the ratio of the soluble nickel salt: the molar ratio of the soluble cobalt salt to the soluble manganese salt is 6-9: 4 to 1.
4. The method for preparing the precursor of the positive electrode material of the lithium ion battery according to claim 2, wherein the total molar concentration of the three salts in the container a is 1-6 mol/L; preferably 2-4 mol/L; the total molar concentration of the five salts in the container b is 1-6 mol/L; preferably 2-4 mol/L;
total molar amount of three salts in the container a: the total molar weight of the five salts in the container b is 7-9: 3-1;
the soluble nickel salt, the soluble cobalt salt, the soluble manganese salt and the soluble magnesium salt are all battery-grade sulfates or nitrates with the valence of +2 corresponding to each other, and the soluble titanium salt is titanyl sulfate or titanium nitrate.
5. The preparation method of the precursor of the positive electrode material of the lithium ion battery according to claim 2, wherein the pH in the step (2) is 11.0-12.5; preferably 11.5 to 12.0;
the addition amount of the glutamic acid is 1-5% of the total addition mole amount of soluble nickel salt, soluble cobalt salt and soluble manganese salt; preferably 2 to 3 percent.
6. The method for preparing the precursor of the positive electrode material of the lithium ion battery according to claim 2, wherein N is obtained in the step (2) and the step (3)2The feeding speed is the same, namely the volume of gas fed in every minute is 0.4-2 reactor volumes.
7. The preparation method of the precursor of the positive electrode material of the lithium ion battery according to claim 2, wherein the ammonia water concentration in the step (2), the step (3) and the step (4) is 1-6 mol/L; preferably 2-4 mol/L; the total molar weight of the ammonia water is 0.2-0.8 times of the total molar weight of the salt; preferably 0.4 to 0.6 times;
the alkali liquor is at least one of sodium hydroxide, sodium carbonate and sodium bicarbonate, and the concentration of the alkali liquor is 2-10 mol/L; preferably 4 to 6 mol/L.
8. The method for preparing the precursor of the positive electrode material of the lithium ion battery according to claim 2, wherein the reaction temperature in the step (2) and the reaction temperature in the step (3) and the reaction temperature in the step (4) are the same and are 40-90 ℃, preferably 50-65 ℃.
9. The method for preparing the precursor of the positive electrode material of the lithium ion battery according to claim 2, wherein the pH in the step (3) is 10.5-11.5.
10. The preparation method of the precursor of the positive electrode material of the lithium ion battery according to claim 2, wherein the pH in the step (4) is 10.5-11.5; the drying temperature is 100 ℃; the dehydration temperature is 600-1000 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010800024.0A CN111933926B (en) | 2020-08-11 | 2020-08-11 | Lithium ion battery anode material precursor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010800024.0A CN111933926B (en) | 2020-08-11 | 2020-08-11 | Lithium ion battery anode material precursor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111933926A true CN111933926A (en) | 2020-11-13 |
| CN111933926B CN111933926B (en) | 2021-06-22 |
Family
ID=73307492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010800024.0A Active CN111933926B (en) | 2020-08-11 | 2020-08-11 | Lithium ion battery anode material precursor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111933926B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113437260A (en) * | 2021-06-29 | 2021-09-24 | 中钢天源股份有限公司 | Single crystal battery anode material and preparation method thereof |
| CN114196829A (en) * | 2021-11-17 | 2022-03-18 | 华中科技大学 | Method for recovering nickel-cobalt-manganese cathode material of retired lithium ion battery |
| CN114214730A (en) * | 2021-12-15 | 2022-03-22 | 中钢天源股份有限公司 | Preparation method of high-capacity single crystal positive electrode battery material and product |
| CN114883522A (en) * | 2022-04-20 | 2022-08-09 | 南京邮电大学 | High-entropy-like multi-element layered transition metal oxide cathode material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170338482A1 (en) * | 2016-05-20 | 2017-11-23 | Korea University Research And Business Foundation | Material of negative electrode for lithium secondary battery |
| CN109052491A (en) * | 2018-07-23 | 2018-12-21 | 安徽工业大学 | A kind of preparation method of the porous high entropy oxide material of lithium ion battery negative material spinel-type |
| CN110364717A (en) * | 2019-07-24 | 2019-10-22 | 东北大学秦皇岛分校 | A kind of high entropy oxide electrode material of spinel-type and preparation method thereof |
| CN110556536A (en) * | 2019-09-19 | 2019-12-10 | 安徽工业大学 | Six-element high-entropy oxide material for lithium ion battery and preparation method thereof |
| CN110600703A (en) * | 2019-09-19 | 2019-12-20 | 安徽工业大学 | Five-element transition metal oxide high-entropy material for lithium ion battery |
| CN111403712A (en) * | 2020-03-27 | 2020-07-10 | 清华大学深圳国际研究生院 | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery |
-
2020
- 2020-08-11 CN CN202010800024.0A patent/CN111933926B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170338482A1 (en) * | 2016-05-20 | 2017-11-23 | Korea University Research And Business Foundation | Material of negative electrode for lithium secondary battery |
| CN109052491A (en) * | 2018-07-23 | 2018-12-21 | 安徽工业大学 | A kind of preparation method of the porous high entropy oxide material of lithium ion battery negative material spinel-type |
| CN110364717A (en) * | 2019-07-24 | 2019-10-22 | 东北大学秦皇岛分校 | A kind of high entropy oxide electrode material of spinel-type and preparation method thereof |
| CN110556536A (en) * | 2019-09-19 | 2019-12-10 | 安徽工业大学 | Six-element high-entropy oxide material for lithium ion battery and preparation method thereof |
| CN110600703A (en) * | 2019-09-19 | 2019-12-20 | 安徽工业大学 | Five-element transition metal oxide high-entropy material for lithium ion battery |
| CN111403712A (en) * | 2020-03-27 | 2020-07-10 | 清华大学深圳国际研究生院 | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery |
Non-Patent Citations (1)
| Title |
|---|
| HONGCHEN，NANQIU，BAOZHENWU，ZHAOMINGYANG，SENSUN，YUANWANG: "A new spinel high-entropy oxide (Mg 0.2 Ti 0.2 Zn 0.2 Cu 0.2 Fe 0.2 ) 3 O 4 with fast reaction kinetics and excellent stability as an anode material for lithium ion batteries", 《RCS ADVANCES》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113437260A (en) * | 2021-06-29 | 2021-09-24 | 中钢天源股份有限公司 | Single crystal battery anode material and preparation method thereof |
| CN113437260B (en) * | 2021-06-29 | 2022-12-13 | 中钢天源股份有限公司 | Single crystal battery anode material and preparation method thereof |
| CN114196829A (en) * | 2021-11-17 | 2022-03-18 | 华中科技大学 | Method for recovering nickel-cobalt-manganese cathode material of retired lithium ion battery |
| CN114214730A (en) * | 2021-12-15 | 2022-03-22 | 中钢天源股份有限公司 | Preparation method of high-capacity single crystal positive electrode battery material and product |
| CN114883522A (en) * | 2022-04-20 | 2022-08-09 | 南京邮电大学 | High-entropy-like multi-element layered transition metal oxide cathode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111933926B (en) | 2021-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111933926B (en) | Lithium ion battery anode material precursor and preparation method thereof | |
| WO2021168600A1 (en) | Prussian blue sodium ion battery positive electrode material having low moisture content, preparation method therefor, and sodium ion battery | |
| JP6395951B2 (en) | Nickel cobalt aluminum precursor material having aluminum element gradient distribution and method for producing positive electrode material | |
| WO2020047725A1 (en) | Prussian blue cathode material having high sodium content, preparation method therefor and application thereof, and sodium ion battery | |
| CN101335348B (en) | Preparing method of lithium ionic cell 5V anode material spherical LiNi0.5Mn1.5O4 | |
| CN111628149A (en) | Gradient-doped high-nickel ternary positive electrode material and preparation method thereof | |
| CN107910531B (en) | Preparation method of high-nickel-base ternary cathode material | |
| CN103490060A (en) | Lithium nickel cobalt manganese positive electrode material and preparation method thereof | |
| CN108269972B (en) | Novel high-voltage lithium cobalt oxide cathode material and preparation method thereof | |
| CN114188536B (en) | Lithium ion battery anode material uniformly coated with MOF and preparation method thereof | |
| CN106257718B (en) | A kind of BN cladding is without cobalt Ni-Mn solid solution nickel hydroxide base anode materials | |
| CN103172118A (en) | Method for preparing spherical cobaltosic oxide and manganese oxide | |
| CN101284684A (en) | Preparing method for nickel-cobalt-lithium manganate precursor of lithium ionic cell positive material | |
| CN101857278B (en) | Method for preparing spherical carbonate | |
| CN103682311A (en) | Preparation method of ternary composite cathode material of lithium ion battery | |
| CN111333126A (en) | Nickel cobalt lithium manganate material precursor, preparation method thereof and nickel cobalt lithium manganate positive electrode material | |
| CN111908519A (en) | High-capacity nickel-rich precursor, positive electrode material and preparation method thereof | |
| CN114335451A (en) | Preparation method of bimetal doped/porous carbon coated ternary positive electrode material | |
| CN109962234B (en) | Concentration gradient single crystal anode material and preparation method thereof | |
| CN111193007A (en) | Lithium manganate material battery positive electrode and preparation method thereof, and lithium manganate battery | |
| CN109524638B (en) | Preparation method of sodium ion conductor coated lithium-rich manganese-based layered cathode material | |
| CN114388758B (en) | Lithium metal oxide positive electrode material with novel composite phase structure, and preparation method and application thereof | |
| CN108598460A (en) | A kind of anode material of lithium battery and preparation method thereof | |
| CN107394188B (en) | Preparation method of hollow spherical niobium oxide electrode material for lithium ion battery | |
| CN113871582B (en) | Nickel-based positive electrode material for sodium ion battery capable of being used for filling conductive material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |