CN113353991B - Lithium removal material and preparation method thereof - Google Patents
Lithium removal material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lithium removal material and a preparation method thereof, wherein the chemical formula of the lithium removal material is Li (9x+2y+z) Mn y Me z O (3y+z) N 2x X 3x (xLi 9 N 2 X 3 ·yLi 2 MnO 3 zA) has the characteristics of stable performance, easy storage, less residual on the surface of the material, high lithium removal capacity and the like; the invention also discloses a preparation method of the lithium removal material, which synthesizes a precursor from a metal salt and a manganese compound by a chemical coprecipitation method, sequentially carries out heat treatment and crushing, and then carries out multi-stage sintering of lithium preparation for a plurality of times to form the lithium removal material, and the method has simple and convenient process, and ensures that Li is obtained by the multi-time lithium preparation sintering 3 N intercalates into the lattice interior of the material, li 9 N 2 X 3 And the co-melt is formed with the substrate material, so that the surface residual is further reduced, the storage and circulation performances of the material are improved, the component performances are complementary and co-exist, and the prepared lithium removal material has the advantages of high lithium removal capacity, small capacity loss and the like.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium removal material, in particular to a high-lithium removal material and a preparation method thereof.
Background
In order to improve the energy density of lithium ion batteries, silicon anode materials with high specific capacity are becoming the choice of battery enterprises and material suppliers, and become one of the most potential anode materials of next generation lithium ion batteries. However, the large volume expansion of silicon cathodes and the low first coulombic efficiency limit their practical application. The coulomb efficiency of the positive electrode material is far higher than that of the negative electrode, so that the capacity of the positive electrode material cannot be fully exerted, and the waste of the positive electrode material and the reduction of the battery capacity are caused. This is mainly because the surface of the negative electrode material forms a solid electrolyte film, i.e., an SEI film, during the first charge, which consumes lithium ions, which are almost entirely provided by the positive electrode material in the battery. Accordingly, a concept of "lithium replenishment" is proposed to replenish lithium ions consumed for forming an SEI film during the first charge of a battery by "lithium replenishment" on a negative electrode, a positive electrode, or a separator.
The process of lithium supplementing of the positive electrode is to add high-lithium capacity materials into the positive electrode in the process of homogenizing the positive electrode, and to supplement irreversible lithium capacity of the first charge and discharge in the process of charging, the surplus lithium elements are separated from the high-lithium capacity positive electrode materials and are inserted into the negative electrode.
Therefore, a lithium source is found out of the positive electrode material, so that lithium ions of the external lithium source are consumed in the formation of the SEI film, the waste of lithium ions extracted from the positive electrode material can be ensured, and the capacity of the full battery can be improved finally. This external lithium source provides lithium in the process of delithiation, and is referred to as delithiation material for the external lithium source on the positive electrode material.
The research of the lithium removal material is a research hotspot in the field of lithium batteries in recent years, patent CN 107221650B mentions a lithium supplementing additive and a preparation method thereof, and the lithium supplementing additive is prepared by mixing a plurality of substances in a certain proportion and sintering the substances in multiple steps, but the purity of the active ingredients is lower, and the particles of partial products have small activity so as to be difficult to store, and the passivation treatment is needed to be carried out again, so that the process is complex. Patent CN 107819113A discloses a lithium supplementing additive, and a preparation method and application thereof, wherein the lithium supplementing additive is used as a core-shell structure, a core material is a conductive carbon material, and a shell material is lithium oxide; the lithium oxide is deposited on the surface of the conductive carbon material, nano-layer shells are formed by nano-sized lithium oxide particles, and the preparation process is complex and difficult. In the prior art and the patent, the preparation method of the lithium removal material has simple process, and the prepared lithium removal material has low purity and low lithium removal capacity and can not completely meet the problem of lithium ion loss of the current lithium ion battery. Therefore, research on a technology with high lithium supplementing capacity and preparation technology suitable for industrialization is an important point of current research.
Disclosure of Invention
The invention mainly aims to overcome the defects of the prior art and provides a lithium removal material and a preparation method thereof, and the lithium removal material has the characteristics of stable performance, easy storage, high lithium removal capacity, small capacity loss and the like.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
according to one aspect of the present invention, there is provided a delithiated material having the formula: li (Li) (9x+2y+z) Mn y Me z O (3y+z) N 2x X 3x (xLi 9 N 2 X 3 •yLi 2 MnO 3 zA), wherein x is more than 0 and less than or equal to 0.25, y is more than 0 and less than or equal to 0.5, z is more than or equal to 0.5 and less than or equal to 1, me is Fe, ni or Co, A contains Li 5 FeO 4 、Li 2 NiO 2 、Li 6 CoO 4 And Li (lithium) 6 MnO 4 X is a group VIIA element.
According to one embodiment of the invention, x, y, z are each integer multiples of 0.05.
According to one embodiment of the invention, X is one or more of F, cl, br, I.
According to another aspect of the present invention, there is provided a method for preparing the above delithiated material, comprising:
s1, preparing a precursor from a metal salt and a manganese compound by a chemical coprecipitation method, and then sequentially carrying out heat treatment, crushing and dispersing in a nitrogen atmosphere;
s2, adding the precursor dispersed in the S1 into metal lithium powder and lithium halide, uniformly mixing and film pressing treatment under nitrogen atmosphere, and sintering in nitrogen under pressure to prepare a sintering material 1;
s3, crushing the sintered material 1 in the step S2;
s4, repeating the steps of S2 and S3 for K times, wherein K is more than or equal to 1, until the lithium removing material is prepared.
According to an embodiment of the invention, the metal salt comprises Li 5 FeO 4 、Li 2 NiO 2 、Li 6 CoO 4 And Li (lithium) 6 MnO 4 One or more of the following.
According to an embodiment of the invention, the manganese compound comprises manganese sulfate, manganese nitrate, manganese chloride or manganese bromide.
According to one embodiment of the invention, the temperature of the heat treatment in S1 is 300-900 ℃.
According to an embodiment of the present invention, the temperature of the heat treatment in S1 is preferably 500 ℃ to 800 ℃.
According to one embodiment of the invention, the time of the heat treatment in S1 is 10 hours to 50 hours.
According to an embodiment of the present invention, the time of the heat treatment in S1 is preferably 20 hours to 40 hours.
According to one embodiment of the invention, the total content of free water and crystal water in the precursor after the heat treatment in S1 is controlled within 0.001% in terms of mole percent.
According to one embodiment of the invention, the molar ratio of the metal lithium powder to the lithium halide is 2:3 to 5:3.
according to an embodiment of the present invention, preferably, the molar ratio of the metal lithium powder to the lithium halide is 2:3 to 3:3.
according to one embodiment of the invention, the total lithium content in the metal lithium powder and the lithium halide is 0.01% -10% higher than the lithium content in the delithiated material in terms of mole percent.
According to an embodiment of the present invention, it is preferable that the total lithium content in the metal lithium powder and the lithium halide is higher than 0.1% -5% of the lithium content in the delithiated material in terms of mole percent.
According to an embodiment of the present invention, the sintering pressurization pressure in S2 and S4 is 10bar to 100bar.
According to an embodiment of the present invention, the sintering pressurization is preferably performed at a pressure of 30bar to 50bar.
According to one embodiment of the invention, the sintering is a multi-stage sintering, with a rapid ramp-up rate V1 to T1 temperature plateau incubation time T1, followed by a rapid ramp-down rate V2 to T2 temperature plateau incubation time T2.
According to one embodiment of the invention, the speed of V1 heating and V2 cooling is not lower than 10 ℃/min, the temperature of T1 is not lower than 700 ℃ and not higher than 950 ℃, the temperature of T2 is not lower than 300 ℃ and not higher than 500 ℃, the temperature of T1 is not lower than 30min and not higher than 120min, and the temperature of T2 is not lower than 5h and not higher than 8h.
According to the embodiment of the invention, the lithium removal material K formed after repeating the steps S2 and S3K times is smaller than the lithium removal material K-1 formed after repeating the steps S2 and S3K-1 times, and the lithium ion battery prepared by taking the lithium removal material K-1 as the positive electrode material has the first lithium removal capacity value difference smaller than 5mAh/g under the condition that the charging voltage is 3-4.5V.
Compared with the prior art, the invention has the beneficial effects that:
1. the lithium removing material of the invention ensures Li to be sintered by multiple lithium matching 3 N intercalates into the lattice interior of the material, li 9 N 2 X 3 Forming eutectic with the substrate material, further reducing surface residual, improving storage and circulation performance of the material, and fully playing Li 3 N is used as the characteristic of a fast ion conductor, and is matched with a base material, and the components are complementary in performance and co-exist together;
2. the lithium removal material obtained by perfecting and optimizing the sintering process has the advantages of stable performance and easy storage; 3. the lithium ion battery prepared by taking the lithium removal material as the positive electrode material has the first lithium removal capacity exceeding 400mAh/g, optimally more than 600mAh/g, and high lithium removal capacity, so that the addition amount can be reduced, and the production cost is further reduced.
Drawings
FIG. 1 is an SEM image of example 11;
fig. 2 is a first charge capacity map of example 11.
Detailed Description
Exemplary embodiments that embody features and advantages of the present invention are described in detail in the following description. It will be understood that the invention is capable of various modifications in various embodiments, all without departing from the scope of the invention, and that the description is intended to be illustrative in nature and not to be limiting.
In one embodiment of the present invention, a lithium removal material is provided, which has the chemical formula: li (Li) (9x+2y+z) Mn y Me z O (3y+z) N 2x X 3x (xLi 9 N 2 X 3 •yLi 2 MnO 3 zA), wherein x is more than 0 and less than or equal to 0.25, y is more than 0 and less than or equal to 0.5, z is more than or equal to 0.5 and less than or equal to 1, me is Fe, ni or Co, A contains Li 5 FeO 4 、Li 2 NiO 2 、Li 6 CoO 4 And Li (lithium) 6 MnO 4 X is a group VIIA element.
In one embodiment of the invention, x, y, z are all integer multiples of 0.05.
In one embodiment of the invention, X is one or more of F, cl, br, I.
The lithium removal material has the advantages of high lithium removal capacity, stable structure, easy storage, small capacity loss and the like.
An embodiment of the present invention provides a method for preparing the above lithium removing material, including:
s1, preparing a precursor from a metal salt and a manganese compound by a chemical coprecipitation method, and then sequentially carrying out heat treatment, crushing and dispersing in a nitrogen atmosphere;
s2, adding the precursor dispersed in the S1 into metal lithium powder and lithium halide, uniformly mixing and film pressing treatment under nitrogen atmosphere, and sintering in nitrogen under pressure to prepare a sintering material 1;
s3, crushing the sintered material 1 in the step S2;
s4 is repeated K times S2 and S3, K is more than or equal to 1, for example, K is 1, 3, 6, 8, 10 and the like, until the lithium removing material is prepared. The lithium ion battery prepared by taking the lithium removal material K formed after repeating the steps S2 and S3K times as the positive electrode material is smaller than the lithium removal material K-1 formed after repeating the steps S2 and S3K-1 times, and the difference of the first lithium removal capacity values of the lithium ion battery is smaller than 5mAh/g under the condition that the charging voltage is 3-4.5V.
In one embodiment of the present invention, the metal salt comprises Li 5 FeO 4 、Li 2 NiO 2 、Li 6 CoO 4 And Li (lithium) 6 MnO 4 One or more of the following.
In one embodiment of the invention, the manganese compound comprises manganese sulfate, manganese nitrate, manganese chloride or manganese bromide.
In one embodiment of the present invention, the temperature of the heat treatment in S1 is 300 ℃ to 900 ℃, for example 300 ℃, 400 ℃, 550 ℃, 600 ℃,700 ℃, 850 ℃, 900 ℃, etc.
In one embodiment of the present invention, the temperature of the heat treatment in S1 is preferably 500 ℃ to 800 ℃, for example 500 ℃, 650 ℃, 750 ℃, 800 ℃, etc.
In one embodiment of the present invention, the time of the heat treatment in S1 is 10 hours to 50 hours, for example, 10 hours, 25 hours, 35 hours, 45 hours, 50 hours, etc.
In one embodiment of the present invention, the time for the heat treatment in S1 is preferably 20 hours to 40 hours, for example, 20 hours, 30 hours, 40 hours, or the like.
In one embodiment of the present invention, the total content of the free water and the crystal water in the precursor after the heat treatment in S1 is controlled to be within 0.001%, for example, 0.001%, 0.0008%, 0.0006%, 0.0004%, 0.0002%, etc., in terms of mole percent.
In one embodiment of the invention, lithium halides, such as LiF, liCl, liBr, liI and the like.
In one embodiment of the invention, the molar ratio of the metal lithium powder to the lithium halide is 2:3 to 5:3, for example molar ratio 2: 3. molar ratio 4: 3. molar ratio 5:3, etc.
In one embodiment of the present invention, preferably, the molar ratio of the metal lithium powder to the lithium halide is 2:3 to 3:3, for example, molar ratio 2.2: 3. molar ratio 2.5: 3. molar ratio 2.8:3, etc.
In one embodiment of the present invention, the total lithium content in the metal lithium powder and the lithium halide is higher than 0.01% -10%, such as 0.01%, 1%, 6%, 10% and the like, of the lithium content in the delithiated material by mole percent.
In one embodiment of the present invention, the total lithium content in the metal lithium powder and the lithium halide is preferably higher than 0.1% -5%, for example 0.1%, 2%, 3%, 4%, 5% or the like of the lithium content in the delithiated material in terms of mole percent.
In an embodiment of the present invention, the sintering pressure in S2 and S4 is 10bar to 100bar, for example, 10bar, 20bar, 60bar, 80bar, 100bar, etc.
In one embodiment of the present invention, the sintering pressure in S2 and S4 is preferably 30bar to 50bar, for example 30bar, 40bar, 50bar, etc.
In one embodiment of the present invention, the sintering is a multi-stage sintering, wherein the temperature is maintained for a period of time T1 from a rapid temperature rise rate V1 to a temperature plateau of T1, and then is maintained for a period of time T2 from a rapid temperature drop rate V2 to a temperature plateau of T2.
In one embodiment of the invention, the V1 temperature increase and V2 temperature decrease rates are not less than 10deg.C/min, such as 10deg.C/min, 20deg.C/min, 30deg.C/min, 50deg.C/min, 100deg.C/min, etc.
In one embodiment of the present invention, T1 is 700 ℃ to 950 ℃, e.g., T1 is 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, etc.
In one embodiment of the present invention, T2 is 300 ℃ or less and 500 ℃ or less, for example T2 is 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, etc.
In one embodiment of the present invention, t1 is 30 min.ltoreq.t1.ltoreq.120 min, for example, t1 is 30min, 50min, 80min, 100min, 120min, etc.
In one embodiment of the present invention, 5 h.ltoreq.t2.ltoreq.8h, for example, t2 is 5h, 6h, 7h, 8h etc.
The preparation method of the lithium removal material has simple and convenient process, and Li is prepared by multiple lithium matching and sintering 3 N intercalates into the lattice interior of the material, li 9 N 2 X 3 Forming eutectic with the substrate material, further reducing surface residual, improving storage and circulation performance of the material, and fully playing Li 3 N is used as a fast ion conductor, and is matched with a base material, the components are complementary in performance and co-exist, so that the prepared lithium removal material has excellent performances such as stable performance and structure, high lithium removal capacity and the like. In the aspect of sintering process, the temperature is firstly increased to be higher than Wen Pingtai, the grain boundary of the material is activated, so that the material can obtain enough energy to generate migration diffusion, the temperature is quickly reduced to a low-temperature section for heat preservation, the material grains are prevented from being oversized, and lithium ions are more fully formedEmbedded in the grain boundary to further improve the material performance.
The lithium removing material and the preparation method thereof according to the present invention are further described below with reference to specific examples.
The embodiment of the invention is carried out according to the following method:
preparing a precursor from a metal salt and a manganese compound by a chemical coprecipitation method, and then sequentially carrying out heat treatment and crushing under a nitrogen atmosphere; adding metal lithium powder and lithium halide into the precursor, uniformly mixing and laminating the mixture under nitrogen atmosphere, sintering the mixture under pressure in nitrogen to prepare a sintered material 1, and crushing the sintered material; repeatedly adding metal lithium powder and lithium halide, uniformly mixing under nitrogen atmosphere, performing film pressing treatment, sintering under nitrogen atmosphere and pressurizing, and crushing until a lithium removal material is formed; the chemical formula of the lithium removing material is Li (9x+2y+z) Mn y Me z O (3y+z) N 2x X 3x (xLi 9 N 2 X 3 •yLi 2 MnO 3 zA), wherein x is more than 0 and less than or equal to 0.25, y is more than 0 and less than or equal to 0.5, z is more than or equal to 0.5 and less than or equal to 1, me is Fe, ni or Co, A contains Li 5 FeO 4 、Li 2 NiO 2 、Li 6 CoO 4 And Li (lithium) 6 MnO 4 X is a group VIIA element.
Example 1
10kg of metal salt was taken as analytically pure Li 2 NiO 2 And analytically pure Li 5 FeO 4 Wherein Li is 2 NiO 2 ：Li 5 FeO 4 The molar ratio is 1:1, a step of; taking 1kg of analytically pure manganese sulfate; li is mixed with 2 NiO 2 And Li (lithium) 5 FeO 4 Preparing 1mol/L sulfate solution from manganese sulfate, adding into a reaction vessel according to the proportion of 5L sulfate solution to 8L 1mol/L sodium hydroxide solution and 0.2L 10mol/L ammonia water, reacting, filtering, washing and drying the precipitate to obtain precursor, and then performing heat treatment and crushing under nitrogen atmosphere, wherein the heat treatment condition is that heating is performed at 700 ℃ for 40 hours, and crushing is performed until the precursor is obtainedMedian particle diameter D5015 μm; adding a mixture of equivalent metal lithium powder and lithium chloride into the crushed precursor, wherein the molar ratio of the metal lithium powder to the lithium chloride is 2:3, uniformly mixing and laminating the materials in a nitrogen atmosphere, sintering the materials in nitrogen under pressure to prepare a sintered material 1, and crushing the sintered material until the median D50 of the particle size is 15 mu m; after repeating for 4 times, 100g of a mixture of metallic lithium powder and lithium chloride is added into the crushed sintered material 1, wherein the molar ratio of the metallic lithium powder to the lithium chloride is 2:3, uniformly mixing and laminating the materials in a nitrogen atmosphere, sintering the materials under pressure in nitrogen, crushing the materials until the median D50 of the particle size is 15 mu m, preparing a lithium-removing material, repeating the process for 4 times to form a lithium-removing material 4, and repeating the process for 3 times to form a lithium-removing material 3 serving as a positive electrode material to prepare the lithium ion battery, wherein under the condition that the charging voltage is 3-4.5V, the difference of the lithium-removing capacity values of the lithium ion battery for the first time is 3mAh/g; the total lithium content in the added metal lithium powder and lithium chloride mixture is higher than the mole percentage of the lithium content in the finally prepared lithium removal material by 0.1%, the above sintering processes are multi-stage sintering, the temperature of the sintering process is maintained for a period of time T1 from a rapid heating speed V1 to a temperature of a T1 temperature platform, and then the sintering is carried out for a period of time T2 from a rapid cooling speed V2 to a temperature of a T2 temperature platform, wherein the sintering pressurization pressure is 30bar, v1=15 ℃/min, t1=800 ℃, t1=60 min, v2=15 ℃/min, t2=400 ℃, and t2=6 h; the chemical formula of the lithium removing material is Li (9x+2y+z) Mn y Me z O (3y+z) N 2x X 3x (xLi 9 N 2 X 3 •yLi 2 MnO 3 zA) wherein x is 0.05, y is 0.25, z is 0.7, me is Fe and Ni, A is Li 2 NiO 2 And Li (lithium) 5 FeO 4 X is Cl.
Example 2
The same preparation as in example 1, except that the metal salt was selected as analytically pure Li 2 NiO 2 And analytically pure Li 5 FeO 4 Wherein Li is 2 NiO 2 ：Li 5 FeO 4 The molar ratio is 4:1, a step of; the lithium removing material 4 formed after repeating for 4 times is used as a positive electrode material compared with the lithium removing material 3 formed after repeating for 3 timesUnder the condition that the charging voltage of the prepared lithium ion battery is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 3.5mAh/g; in the delithiated material, x is 0.05, y is 0.35, and z is 0.6.
Example 3
The same preparation as in example 1, except that the metal salt was selected as analytically pure Li 2 NiO 2 And analytically pure Li 5 FeO 4 Wherein Li is 2 NiO 2 ：Li 5 FeO 4 The molar ratio is 3:2; the lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and under the condition that the charging voltage is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 3.6mAh/g; in the delithiated material, x is 0.1, y is 0.25, and z is 0.65.
Example 4
The same preparation as in example 1, except that the metal salt was selected as analytically pure Li 2 NiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and under the condition that the charging voltage is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 4.3mAh/g; in the lithium removing material, x is 0.15, y is 0.35, z is 0.5, me is Ni, A is Li 2 NiO 2 。
Example 5
The same preparation as in example 1, except that the metal salt was selected as analytically pure Li 2 NiO 2 And analytically pure Li 5 FeO 4 Wherein Li is 2 NiO 2 ：Li 5 FeO 4 The molar ratio is 2:3, a step of; the lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and the difference of the first lithium removal capacity values of the lithium ion battery is 4mAh/g under the condition that the charging voltage is 3-4.5V; in the delithiated material, x is 0.2, y is 0.15, and z is 0.65.
Example 6
The same preparation as in example 1, except thatThe metal salt is analytically pure Li 5 FeO 4 (II), (III), (V), (; the lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and under the condition that the charging voltage is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 3.9mAh/g; in the lithium removing material, x is 0.2, y is 0.25, z is 0.55, me is Fe, A is Li 5 FeO。
Example 7
The same preparation as in example 1, except that the heat treatment condition was 600℃for 20 hours; adding a mixture of equivalent metal lithium powder and lithium bromide into the crushed precursor, wherein the molar ratio of the metal lithium powder to the lithium bromide is 2.5:3, a step of; the lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and under the condition that the charging voltage is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 3.8mAh/g; the sintering pressurization pressure is 40bar, v1=15 ℃/min, t1=700 ℃, t1=90 min, v2=15 ℃/min, t2=450 ℃, t2=6 h; in the lithium removing material, X is Br.
Example 8
The same preparation as in example 1, except that the heat treatment condition was 600℃for 20 hours; adding a mixture of equivalent metal lithium powder and lithium iodide into the crushed precursor, wherein the molar ratio of the metal lithium powder to the lithium iodide is 2.5:3, a step of; the lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and under the condition that the charging voltage is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 2.5mAh/g; the total lithium content in the metal lithium powder and the lithium iodide is 0.5 percent by mole higher than the lithium content in the delithiated material; the lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and under the condition that the charging voltage is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 4.5mAh/g; the sintering pressurization pressure is 50bar, v1=15 ℃/min, t1=750 ℃, t1=90 min, v2=15 ℃/min, t2=550 ℃, t2=7 h; in the lithium removing material, X is I.
Example 9
The same preparation as in example 1, except that the metal salt was selected as analytically pure Li 2 NiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Adding a mixture of equivalent metal lithium powder and lithium chloride into the crushed precursor, wherein the molar ratio of the metal lithium powder to the lithium chloride is 2.5:3, a step of; the lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and under the condition that the charging voltage is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 4.6mAh/g; the total lithium content in the metal lithium powder and the lithium iodide is 0.3 percent by mole higher than the lithium content in the delithiated material; the sintering pressurization pressure is 30bar, v1=15 ℃/min, t1=750 ℃, t1=60 min, v2=15 ℃/min, t2=500 ℃, t2=5 h; in the lithium removing material, x is 0.05, y is 0.25, z is 0.7, me is Ni, A is Li 2 NiO 2 。
Example 10
The same preparation as in example 9, except that the metal salt was selected as analytically pure Li 2 NiO 2 And analytically pure Li 5 FeO 4 Wherein Li is 2 NiO 2 ：Li 5 FeO 4 The molar ratio is 4:1, a step of; the lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and under the condition that the charging voltage is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 4.7mAh/g; in the delithiated material, x is 0.05, y is 0.35, and z is 0.6.
Example 11
The same preparation as in example 9, except that the metal salt was selected as analytically pure Li 2 NiO 2 And analytically pure Li 5 FeO 4 Wherein Li is 2 NiO 2 ：Li 5 FeO 4 The molar ratio is 3:2; in the delithiated material, wherein x is 0.1, y is 0.25, z is 0.65, A is Li 2 NiO 2 And Li (lithium) 5 FeO 4 。
Example 12
The same preparation as in example 9, except thatThe metal salt is analytically pure Li 2 NiO 2 And analytically pure Li 5 FeO 4 Wherein Li is 2 NiO 2 ：Li 5 FeO 4 Is 1:1 of mole ratio; the lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and under the condition that the charging voltage is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 4.5mAh/g; in the delithiated material, x is 0.15, y is 0.35, and z is 0.5.
Example 13
The same preparation as in example 9, except that the metal salt was selected as analytically pure Li 2 NiO 2 And analytically pure Li 5 FeO 4 Wherein Li is 2 NiO 2 ：Li 5 FeO 4 The molar ratio is 2:3, a step of; the lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and under the condition that the charging voltage is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 3.8mAh/g; in the delithiated material, x is 0.2, y is 0.15, and z is 0.65.
Example 14
The same preparation as in example 9, except that the metal salt was selected as analytically pure Li 5 FeO 4 Is a mixture of (a) and (b); the lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and under the condition that the charging voltage is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 3.7mAh/g; in the lithium removing material, x is 0.2, y is 0.25, z is 0.55, me is Fe, A is Li 5 FeO 4 。
Example 15
The same preparation as in example 1, except that the heat treatment condition was 800℃for 30 hours; adding equivalent metal lithium powder and lithium fluoride into the crushed precursor, wherein the molar ratio of the metal lithium powder to the lithium fluoride is 3:3, a step of; the lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and under the condition that the charging voltage is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 3.5mAh/g; the total lithium content in the metal lithium powder and the lithium fluoride is 0.5 percent by mole higher than the lithium content in the delithiated material; the sintering pressurization pressure is 100bar, v1=15 ℃/min, t1=900 ℃, t1=100 min, v2=15 ℃/min, t2=500 ℃, t2=8 h; in the delithiated material, X is F.
Example 16
The same preparation as in example 1, except that the metal salt was selected as analytically pure Li 6 CoO 4 And analytically pure Li 6 MnO 4 Wherein Li is 6 CoO 4 ：Li 6 MnO 4 The molar ratio is 1:1, a step of; heating at 700 ℃ for 30 hours; adding equivalent metal lithium powder and lithium chloride into the crushed precursor, wherein the molar ratio of the metal lithium powder to the lithium chloride is 3:3, a step of; the lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and under the condition that the charging voltage is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 4.1mAh/g; the total lithium content in the metal lithium powder and the lithium chloride is 0.5 percent higher than the molar percentage of the lithium content in the lithium removal material; the sintering pressurization pressure is 100bar, v1=15 ℃/min, t1=900 ℃, t1=100 min, v2=15 ℃/min, t2=500 ℃, t2=8 h; in the lithium removing material, me is Co, A is Li 6 CoO 4 And Li (lithium) 6 MnO 4 。
Comparative example 1
10kg of metal salt was taken as analytically pure Li 2 NiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Taking 1kg of analytically pure manganese sulfate; li is mixed with 2 NiO 2 Adding the mixture into a reaction vessel to react with manganese sulfate serving as a raw material to prepare a sulfate solution with the concentration of 1mol/L, adding the sulfate solution with the concentration of 8L of a sodium hydroxide solution with the concentration of 1mol/L and the concentration of 0.2L of 10mol/L ammonia water into the reaction vessel according to the proportion, filtering, washing and drying a precipitate to prepare a precursor, and then performing heat treatment and crushing under nitrogen atmosphere, wherein the heat treatment condition is that the heating is carried out at 600 ℃ for 30 hours; crushing until the median D50 of the particle size of the precursor is 15 mu m; adding a mixture of equivalent amounts of metallic lithium powder and lithium chloride to the crushed precursor, wherein goldThe molar ratio of the lithium powder to the lithium chloride is 2:3, uniformly mixing and laminating the materials in a nitrogen atmosphere, sintering the materials in nitrogen under pressure to prepare a sintered material 1, and crushing the sintered material until the median D50 of the particle size is 15 mu m; after repeating for 4 times, 100g of a mixture of metallic lithium powder and lithium chloride is added into the crushed sintered material 1, wherein the molar ratio of the metallic lithium powder to the lithium chloride is 2:3, uniformly mixing and laminating the materials under nitrogen atmosphere, sintering the materials under pressure in nitrogen, crushing the materials until the median D50 of the particle size is 15 mu m, preparing a lithium-removed material, repeating the process for 4 times to form a lithium-removed material 4, and taking the lithium-removed material 3 formed after repeating the process for 3 times as a lithium ion battery prepared by taking the positive electrode material, wherein under the condition that the charging voltage is 3-4.5V, the difference of the lithium-removed capacity values of the lithium ion battery is 25mAh/g for the first time, and the total lithium content in the mixture of the added metal lithium powder and lithium chloride is higher than the molar percentage of the lithium content in the finally prepared lithium-removed material by 0.2%; the sintering process is not provided with a plurality of sections of sintering platforms, the temperature of the rapid heating speed V1 to T1 is kept for the heat preservation time T1, the sintering pressurization pressure is 30bar, v1=15 ℃/min, t1=800 ℃, and t1=12 h; the chemical formula of the lithium removing material is Li (9x+2y+z) Mn y Me z O (3y+z) N 2x X 3x (xLi 9 N 2 X 3 •yLi 2 MnO 3 zA) wherein x is 0.05, y is 0.25, z is 0.7, me is Ni, A is Li 2 NiO 2 X is Cl.
Comparative example 2
The same preparation as in comparative example 1, except that the metal salt was selected as analytically pure Li 2 NiO 2 And analytically pure Li 5 FeO 4 Mixtures in which Li 2 NiO 2 ：Li 5 FeO 4 The molar ratio is 4:1, a step of; the lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and under the condition that the charging voltage is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 21mAh/g; in the lithium removing material, x is 0.05, y is 0.35, z is 0.6, me is Ni and Fe, A is Li 2 NiO 2 And Li (lithium) 5 FeO 4 。
Comparative example 3
The same preparation as in comparative example 1, except that the metal salt was selected as analytically pure Li 2 NiO 2 And analytically pure Li 5 FeO 4 Mixtures in which Li 2 NiO 2 ：Li 5 FeO 4 The molar ratio is 3:2; lithium ion battery prepared by taking lithium removal material 4 formed after repeating for 4 times as positive electrode material compared with lithium removal material 3 formed after repeating for 3 times, wherein under the condition that charging voltage is 3-4.5V, the difference of lithium removal capacity values of the lithium ion battery is 18mAh/g, wherein x is 0.1, y is 0.25, z is 0.65, me is Ni and Fe, A is Li 2 NiO 2 And Li (lithium) 5 FeO 4 。
Comparative example 4
The same preparation as in comparative example 1, except that the metal salt selected was Li 5 FeO 4 The method comprises the steps of carrying out a first treatment on the surface of the The lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times and the lithium removal material 3 formed after repeating for 3 times as the positive electrode material has the first lithium removal capacity value difference of 29mAh/g in the lithium removal material under the condition of charging voltage of 3-4.5V, wherein x is 0.2, y is 0.25, z is 0.55, me is Fe, and A is Li 5 FeO 4 。
Comparative example 5
The same preparation as in comparative example 1, except that the heat treatment condition was heating at 800℃for 30 hours; adding a mixture of equivalent metal lithium powder and lithium chloride into the crushed precursor, wherein the ratio of the metal lithium powder to the lithium chloride is 3:3, a step of; the lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and under the condition that the charging voltage is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 26mAh/g; wherein the metal lithium powder also comprises lithium carbonate and lithium hydroxide powder; the total lithium content in the metal lithium powder and the lithium chloride is 0.5 percent higher than the molar percentage of the lithium content in the lithium removal material; setting a multi-stage sintering platform, wherein the sintering process is carried out at the sintering pressure of 30bar, T1=900 ℃, T2=500 ℃, t1=100 min and t2=8 h, and repeating the sintering for 4 times.
Comparative example 6
The same preparation as in comparative example 1, except that the heat treatment condition was heating at 800℃for 30 hours; adding equal amount of a mixture of metal lithium powder and lithium chloride into the crushed precursor, wherein the molar ratio of the metal lithium powder to the lithium chloride is 3:3, a step of; the lithium ion battery prepared by taking the lithium removal material 4 formed after repeating for 4 times as the positive electrode material is compared with the lithium removal material 3 formed after repeating for 3 times, and under the condition that the charging voltage is 3-4.5V, the difference of the first lithium removal capacity values of the lithium ion battery is 31mAh/g; wherein the metal lithium powder also comprises lithium carbonate and lithium hydroxide powder; the total lithium content in the metal lithium powder and the lithium chloride is 0.5 percent higher than the molar percentage of the lithium content in the lithium removal material; setting a multi-stage sintering platform, wherein the sintering process is carried out at the sintering pressure of 30bar, T1=900 ℃, T2=500 ℃, t1=100 min and t2=8 h, and repeating the sintering for 4 times, wherein x is 0.2, y is 0.3 and z is 0.5.
In the embodiment or the comparative example, a lithium ion battery prepared by taking a sample as a lithium battery anode material, graphite as a lithium battery cathode material and an ethyl carbonate solution of lithium hexafluorophosphate as an electrolyte is measured according to YS/T798-2012 of lithium nickel cobalt manganese oxide with a primary charging capacity of 3-4.5V.
The first charge capacity of the non-stored sample was subtracted from the first charge capacity of the sample stored for 5 days at a dew point of-50 ℃ and stored for 10 hours at a relative humidity of 10%, respectively, to obtain a capacity loss of the sample stored for 5 days at a dew point of-50 ℃ and a capacity loss of the sample stored for 10 hours at a relative humidity of 10%.
The test results of the test experiments of examples 1 to 14 and comparative examples 1 to 4 are shown in table 1, wherein the lithium ion batteries tested under the condition that the charging voltage is 3 to 4.5v are used as the positive electrode materials for the first lithium removal capacity, and the lithium ion batteries are tested under the condition that the lithium ion batteries are stored for 5 days at the dew point of-50 ℃ in a drying manner and stored for 10 hours at the relative humidity of 10%.
TABLE 1 test results of first lithium removal Capacity and Capacity loss test
As can be seen from Table 1, the lithium ion batteries prepared by the lithium removal materials prepared in examples 1-6 and examples 9-14 have the first lithium removal capacity exceeding 400mAh/g and the best performance reaching 631mAh/g; in contrast, the first lithium removal capacity of comparative examples 1-4 can only reach 350mAh/g at the highest; therefore, the lithium removal material has the advantage of high lithium removal capacity. Meanwhile, the capacity loss under the conditions of 5 days of dry storage at the dew point of 50 ℃ below zero and 10 hours of storage at the relative humidity of 10% is tested, the capacity loss of examples 1-6 and examples 9-14 is far lower than that of comparative examples 1-4, and the lithium removal material has the excellent performance of stable performance and easy storage from the practical point of view. It will be appreciated by persons skilled in the art that the embodiments described herein are merely exemplary and that various other alternatives, modifications and improvements may be made within the scope of the invention. Thus, the present invention is not limited to the above-described embodiments, but only by the claims.
Claims (15)
1. The lithium removing material is characterized by having the chemical formula: xLi 9 N 2 X 3 ·yLi 2 MnO 3 zA, wherein 0 < x.ltoreq.0.25, 0 < y.ltoreq.0.5, 0.5.ltoreq.z.ltoreq.1, me is Fe, ni or Co, A is selected from Li 5 FeO 4 、Li 2 NiO 2 、Li 6 CoO 4 And Li (lithium) 6 MnO 4 X is a group VIIA element.
2. The delithiated material of claim 1, wherein x, y, z are each an integer multiple of 0.05.
3. The delithiated material of claim 1, wherein X is selected from one or more of F, cl, br, and I.
4. A method of preparing a delithiated material according to any one of claims 1 to 3, said method comprising:
s1, preparing a precursor from a metal salt and a manganese compound by a chemical coprecipitation method, and then sequentially carrying out heat treatment, crushing and dispersing in a nitrogen atmosphere; the metal salt is selected from Li 5 FeO 4 、Li 2 NiO 2 、Li 6 CoO 4 And Li (lithium) 6 MnO 4 One or more of the following;
s2, adding the dispersed precursor in the step S1 into metal lithium powder and lithium halide, uniformly mixing and laminating the mixture under nitrogen atmosphere, and then sintering the mixture under nitrogen and pressure to prepare a sintering material 1;
s3, crushing the sintering material 1 in the step S2;
s4, repeating the steps of S2 and S3 for K times, wherein K is more than or equal to 1, until the lithium removing material is prepared.
5. The method of claim 4, wherein the manganese compound comprises manganese sulfate, manganese nitrate, manganese chloride, or manganese bromide.
6. The method according to claim 4, wherein the temperature of the heat treatment in S1 is 300-900 ℃ and the heat treatment time is 10-50 h.
7. The method according to claim 6, wherein the temperature of the heat treatment in S1 is 500-800 ℃ and the heat treatment time is 20-40 h.
8. The method according to claim 4, wherein the total content of free water and crystal water in the precursor after the heat treatment in S1 is controlled to be within 0.001% in terms of the massage percentage.
9. The method according to claim 4, wherein the ratio of the metal lithium powder to the lithium halide is 2:3 to 5:3.
10. the method according to claim 9, wherein the ratio of the metal lithium powder to the lithium halide is 2:3 to 3:3.
11. the method of claim 4, wherein the total lithium content of the metal lithium powder and the lithium halide is 0.01 to 10% higher than the lithium content of the delithiated material by mole percent.
12. The method of claim 11, wherein the total lithium content of the metallic lithium powder and the lithium halide is 0.1 to 5% by mole higher than the lithium content of the delithiated material.
13. The method according to claim 4, wherein the sintering pressurization in S2 and S4 is 10bar to 100bar.
14. The method of claim 4, wherein the sintering is a multi-stage sintering, wherein the temperature is raised to T1 at a temperature raising speed V1, the temperature is kept for a temperature platform for a period of time T1, then the temperature is lowered to T2 at a temperature lowering speed V2, the temperature is kept for a period of time T2 at the temperature platform, the temperature of the V1 is raised to not lower than 10 ℃/min, the temperature of the V2 is not lower than 700 ℃ and not higher than 950 ℃, the temperature of the T2 is not higher than 300 ℃ and not higher than 500 ℃, the temperature of the T1 is not higher than 30min and not higher than 120min, and the temperature of the T2 is not higher than 5h and not higher than 8h.
15. The method of claim 4, wherein the lithium ion battery prepared by using the lithium removal material K formed after repeating the steps of S2 and S3K times is smaller than the lithium removal material K-1 formed after repeating the steps of S2 and S3K-1 times as the positive electrode material, and the difference of the lithium ion battery primary lithium removal capacity values is smaller than 5mAh/g under the condition that the charging voltage is 3-4.5V.
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