CN113353991A - Lithium removal material and preparation method thereof - Google Patents
Lithium removal material and preparation method thereof Download PDFInfo
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- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
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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)MnyMezO(3y+z)N2xX3x(xLi9N2X3·yLi2MnO3zA), has the characteristics of stable performance, easy storage, less material surface residue, high lithium removal capacity and the like; the invention also discloses a preparation method of the lithium removal material, which synthesizes metal salt and manganese compound by a chemical coprecipitation methodThe precursor is heat treated, crushed and sintered to form lithium eliminating material3N being embedded within the material lattice, Li9N2X3The lithium-removing material and a substrate material form a eutectic body, so that the surface residue is further reduced, the storage and cycle performance of the material is improved, the performances of the components are complementary and coexist synergistically, and the prepared lithium-removing material has the advantages of high lithium-removing capacity, small capacity loss and the like.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, particularly relates to a lithium removal material, and particularly relates to a high lithium removal material and a preparation method thereof.
Background
In order to improve the energy density of the lithium ion battery, a silicon negative electrode material with high specific capacity is gradually becoming the choice of battery enterprises and material suppliers, and becomes one of the most potential next-generation lithium ion battery negative electrode materials. However, the large volume expansion and low first coulombic efficiency of silicon anodes limit their practical applications. Because the coulombic efficiency of the cathode material is far higher than that of the cathode, the capacity of the cathode material cannot be fully exerted, and the waste of the cathode material and the reduction of the battery capacity are caused. This is mainly because the surface of the anode material forms a solid electrolyte film, i.e., an SEI film, during the first charge, which consumes lithium ions, while in the battery, lithium ions are almost entirely supplied from the cathode material. Therefore, the concept of "lithium replenishment" has been proposed to replenish lithium ions consumed by the SEI film formation during the first charge of the battery by "replenishing lithium" on the negative electrode, positive electrode or separator.
The positive pole lithium supplementing process is that during the homogenization of the positive pole, high lithium capacity material is added, and during the charging process, the surplus lithium element is extracted from the high lithium capacity positive pole material and is inserted into the negative pole to supplement the irreversible lithium capacity of the first charge and discharge.
Therefore, a lithium source is found from the outside of the positive electrode material, and lithium ions of the external lithium source are consumed in the formation of the SEI film, so that the waste of the lithium ions deintercalated from the positive electrode material can be ensured, and the full battery capacity can be improved finally. This external lithium source provides the lithium, i.e., delithiation, and is used on the positive electrode material and is referred to as a delithiation material.
The research of the lithium removal material is a research hotspot in the field of lithium batteries in recent years, and patent CN 107221650B discloses a lithium supplement additive and a preparation method thereof, wherein the lithium supplement additive is prepared by mixing a plurality of substances in a certain proportion and sintering in multiple steps, but the purity of active ingredients is low, partial products are small in particle and high in activity, so that the storage is difficult, passivation treatment is required, and the process is complex. Patent CN 107819113a discloses a lithium supplement additive, its preparation method and application, wherein the lithium supplement additive is a core-shell structure, the core material is conductive carbon material, and the shell material is lithium oxide; the lithium oxide is deposited on the surface of the conductive carbon material, and the nano-layer shell is formed by the lithium oxide particles with the nano-size, so the preparation process is complex and has high difficulty.
In the prior art and patents, the preparation method of the lithium removal material is simple in process, and the prepared lithium removal material is low in purity and low in lithium removal capacity and cannot completely meet the problem of lithium ion loss of the current lithium ion battery. Therefore, research on a technology with high lithium supplement capacity and a preparation process suitable for industrialization is a major research point at present.
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.
In order to achieve the purpose, the invention adopts the following technical scheme:
according to one aspect of the present invention, there is provided a delithiating material having the formula: li(9x+2y+z)MnyMezO(3y+z)N2xX3x(xLi9N2X3·yLi2MnO3zA), where x is greater than 0 and less than or equal to 0.25, y is greater than 0 and less than or equal to 0.5, z is greater than or equal to 0.5 and less than or equal to 1, Me is Fe, Ni or Co, A contains Li5FeO4、Li2NiO2、Li6CoO4And Li6MnO4And X is a group viia element.
According to an embodiment of the present invention, x, y, and z are each integer multiples of 0.05.
According to an embodiment of the present invention, X is one or more selected from F, Cl, Br, and I.
According to another aspect of the present invention, there is provided a method for preparing the above delithiation 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 dispersed precursor in S1 into lithium metal powder and lithium halide, uniformly mixing in a nitrogen atmosphere, pressing a film, and sintering in nitrogen under pressure to prepare a sintering material 1;
s3, crushing the sintering material 1 in the S2;
s4 repeating the steps S2 and S3K times, wherein K is more than or equal to 1, until the lithium-removing material is prepared.
According to an embodiment of the present invention, the metal salt contains Li5FeO4、Li2NiO2、Li6CoO4And Li6MnO4One or more of (a).
According to an embodiment of the invention, the manganese compound comprises manganese sulfate, manganese nitrate, manganese chloride or manganese bromide.
According to an embodiment of the present invention, the temperature of the heat treatment in S1 is 300 to 900 ℃.
According to an embodiment of the present invention, it is preferable that the temperature of the heat treatment in S1 is 500 to 800 ℃.
According to an embodiment of the present invention, the heat treatment time in S1 is 10 hours to 50 hours.
According to an embodiment of the present invention, it is preferable that the heat treatment time in S1 is 20 hours to 40 hours.
According to an embodiment of the present invention, the total content of free water and crystal water in the precursor after heat treatment in S1 is controlled within 0.001 mol%.
According to an embodiment of the present invention, the ratio of the halide of the lithium metal powder and the lithium is 2: 3 to 5: 3.
according to an embodiment of the present invention, preferably, the ratio of the metal lithium powder to the lithium halide is 2: 3 to 3: 3.
according to one embodiment of the present invention, the total lithium content of the lithium metal powder and the lithium halide is higher than 0.01 to 10% of the lithium content of the delithiation material in terms of molar percentage.
According to an embodiment of the present invention, it is preferable that the total content of lithium in the lithium metal powder and the lithium halide is higher than 0.1% to 5% of the content of lithium in the delithiation material in terms of mole%.
According to an embodiment of the present invention, the sintering pressures in S2 and S4 are 10bar to 100 bar.
According to an embodiment of the present invention, it is preferable that the sintering pressurization pressure is 30bar to 50 bar.
According to an embodiment of the present invention, the sintering is a multi-stage sintering, which is performed at a fast temperature-raising speed V1 to T1 for a heat-preserving time T1, and then at a fast temperature-lowering speed V2 to T2 for a heat-preserving time T2.
According to an embodiment of the invention, the speed of temperature rise of V1 and temperature drop of V2 is not less than 10 ℃/min, T1 is more than or equal to 700 ℃ and less than or equal to 950 ℃, T2 is more than or equal to 300 ℃ and less than or equal to 500 ℃, T1 is more than or equal to 30min and less than or equal to 120min, and T2 is more than or equal to 5h and less than or equal to 8 h.
According to an embodiment of the invention, the lithium removal material K formed after the repetition of the steps of S2 and S3 for K times is less than that of the lithium ion battery prepared by taking the lithium removal material K-1 formed after the repetition of the steps of S2 and S3 for K-1 times as a positive electrode material, and the difference of the first lithium removal capacity value of the lithium ion battery is less 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 leads Li to be sintered by matching lithium for many times3N being embedded within the material lattice, Li9N2X3Forming eutectic body with the substrate material, further reducing surface residue, improving material storage and circulation performance, and fully exerting Li3N is used as the characteristic of a fast ion conductor and matched with a substrate material, and the components have complementary performance and coexist cooperatively;
2. by perfecting and optimizing the sintering process, the obtained lithium-removing material has the advantages of stable performance and easiness in storage;
3. the lithium removal capacity of the lithium ion battery prepared by taking the lithium removal material as the cathode material exceeds 400mAh/g and is optimally over 600mAh/g for the first time, and the lithium removal capacity is high, so that the addition amount can be reduced, and the production cost is further reduced.
Drawings
FIG. 1 is an SEM photograph 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 invention are described in detail below. It is to be understood that the invention is capable of other and different embodiments and its several details are capable of modification without departing from the scope of the invention, and that the description is intended to be illustrative in nature and not to be construed as limiting the invention.
In one embodiment of the present invention, a lithium-removing material is provided, which has a chemical formula: li(9x+2y+z)MnyMezO(3y+z)N2xX3x(xLi9N2X3·yLi2MnO3zA), where x is greater than 0 and less than or equal to 0.25, y is greater than 0 and less than or equal to 0.5, z is greater than or equal to 0.5 and less than or equal to 1, Me is Fe, Ni or Co, A contains Li5FeO4、Li2NiO2、Li6CoO4And Li6MnO4And X is a group viia element.
In one embodiment of the present invention, x, y, and z are all integer multiples of 0.05.
In one embodiment of the present invention, X includes one or more of F, Cl, Br, and I.
The lithium removing material has the advantages of high lithium removing capacity, stable structure, easy storage, small capacity loss and the like.
In an embodiment of the present invention, there is provided a method for preparing the above delithiation 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 dispersed precursor in S1 into lithium metal powder and lithium halide, uniformly mixing in a nitrogen atmosphere, pressing a film, and sintering in nitrogen under pressure to prepare a sintering material 1;
s3, crushing the sintering material 1 in the S2;
s4 is repeated K times S2 and S3, K ≧ 1, e.g., K of 1, 3, 6, 8, 10, etc., until a delithiated material is prepared. Compared with a lithium ion battery prepared by taking the lithium removal material K formed after the steps of repeating the steps of K times of S2 and S3 as an anode material, the lithium ion battery prepared by taking the lithium removal material K formed after the steps of K-1 times of S2 and S3 as an anode material has the first lithium removal capacity value difference of less than 5mAh/g under the condition that the charging voltage is 3-4.5V.
In one embodiment of the present invention, the metal salt contains Li5FeO4、Li2NiO2、Li6CoO4And Li6MnO4One or more of (a).
In one embodiment of the present 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 ℃.
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 ℃ or the like.
In one embodiment of the present invention, the heat treatment time in S1 is 10 hours to 50 hours, for example, 10 hours, 25 hours, 35 hours, 45 hours, 50 hours, and the like.
In one embodiment of the present invention, the heat treatment time in S1 is preferably 20 hours to 40 hours, for example, 20 hours, 30 hours, 40 hours, and the like.
In an embodiment of the present invention, the total content of free water and crystal water in the precursor after heat treatment in S1 is controlled to be within 0.001%, for example, 0.001%, 0.0008%, 0.0006%, 0.0004%, 0.0002%, or the like, in terms of mole%.
In one embodiment of the present invention, the halide of lithium is, for example, LiF, LiCl, LiBr, LiI, or the like.
In one embodiment of the present invention, the ratio of the halide of lithium metal powder to the halide of lithium is 2: 3 to 5: 3, e.g. in a molar ratio of 2: 3. the molar ratio is 4: 3. the molar ratio is 5: 3, etc.
In one embodiment of the present invention, the ratio of the metal lithium powder and the lithium halide is preferably 2: 3 to 3: 3, for example, in a molar ratio of 2.2: 3. the molar ratio is 2.5: 3. the molar ratio is 2.8: 3, etc.
In one embodiment of the present invention, the total lithium content of the lithium metal powder and the lithium halide is higher than 0.01% to 10%, for example, 0.01%, 1%, 6%, 10% or the like of the lithium content in the delithiating material in terms of mole%.
In one embodiment of the present invention, the total lithium content of the lithium metal powder and the lithium halide is preferably higher than 0.1% to 5%, for example, 0.1%, 2%, 3%, 4%, 5% or the like of the lithium content in the delithiating material in terms of mole%.
In one embodiment of the present invention, the sintering pressures in S2 and S4 are 10bar to 100bar, such as 10bar, 20bar, 60bar, 80bar, 100bar, etc.
In one embodiment of the present invention, it is preferable that the sintering pressures in S2 and S4 are 30bar to 50bar, such as 30bar, 40bar, 50bar, etc.
In one embodiment of the present invention, the sintering is a multi-stage sintering, which is performed at a fast temperature-raising speed V1 to T1 for a thermal-insulation time T1, and then at a fast temperature-lowering speed V2 to T2 for a thermal-insulation time T2.
In one embodiment of the present invention, the V1 temperature rise and V2 temperature fall rates are not less than 10 ℃/min, such as 10 ℃/min, 20 ℃/min, 30 ℃/min, 50 ℃/min, 100 ℃/min, and the like.
In one embodiment of the present invention, T1 is 700 ℃ to 950 ℃, for example T1 is 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ or the like.
In one embodiment of the invention, T2 is 300 ℃ to 500 ℃ such as T2 is 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ and the like.
In one embodiment of the present invention, t1 is not less than 30min and not more than 120min, for example, t1 is 30min, 50min, 80min, 100min, 120min, etc.
In one embodiment of the present invention, t2 is 5h ≦ 8h, for example, t2 is 5h, 6h, 7h, 8h, etc.
The preparation method of the lithium removal material has simple and convenient process, and leads Li to be sintered by matching lithium for many times3N being embedded within the material lattice, Li9N2X3Forming eutectic body with the substrate material, further reducing surface residue, improving material storage and circulation performance, and fully exerting Li3The characteristics of the N as a fast ion conductor are matched with the substrate material, and the components have complementary and synergistic coexistence, so that the prepared lithium removal material has excellent performances of stable performance structure, high lithium removal capacity and the like. In the aspect of a sintering process, the temperature is firstly raised to a high-temperature platform, the grain boundary of the material is activated, the material obtains enough energy to carry out migration and diffusion, the temperature is quickly reduced to a low-temperature section for heat preservation, the grains of the material are prevented from being too large, lithium ions are more fully embedded into the grain boundary, and the performance of the material is further improved.
The lithium-removing material and the preparation method thereof according to the present invention will be further described with reference to the following embodiments.
The examples of the invention were carried out as follows:
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 in a nitrogen atmosphere; adding metal lithium powder and lithium halide into a precursor, uniformly mixing under the nitrogen atmosphere, pressing a film, sintering in nitrogen under pressure to prepare a sintering material 1, and crushing; repeatedly adding metal lithium powder and lithium halide, uniformly mixing in a nitrogen atmosphere, pressing a film, sintering under pressurization in the nitrogen atmosphere, and crushing until a lithium removal material is formed; the chemical formula of the lithium removing material is Li(9x+2y+z)MnyMezO(3y+z)N2xX3x(xLi9N2X3·yLi2MnO3zA), where x is greater than 0 and less than or equal to 0.25, y is greater than 0 and less than or equal to 0.5, z is greater than or equal to 0.5 and less than or equal to 1, Me is Fe, Ni or Co, A contains Li5FeO4、Li2NiO2、Li6CoO4And Li6MnO4Is one or more of, X is the secondA group VIIA element.
Example 1
10kg of metal salt was taken as analytically pure Li2NiO2And analytically pure Li5FeO4In which Li2NiO2：Li5FeO4In a molar ratio of 1: 1; taking 1kg of analytically pure manganese sulfate; mixing Li2NiO2And Li5FeO4The mixture and manganese sulfate are used as raw materials to prepare 1mol/L sulfate solution, 5L of sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water are added into a reaction container to react, the precipitate is filtered, washed and dried to prepare a precursor, and then the precursor is subjected to heat treatment and crushing in a nitrogen atmosphere, wherein the heat treatment condition is that the precursor is heated at 700 ℃ for 40 hours and crushed to the median particle size D5015 mu m of the precursor; adding a mixture of equal amounts 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 2: 3, uniformly mixing in a nitrogen atmosphere, pressing a film, sintering in nitrogen under pressure to prepare a sintering material 1, and crushing until the median D50 of the particle size is 15 microns; and repeating the steps for 4 times, and adding 100g of a mixture of lithium metal powder and lithium chloride into the crushed sintering material 1, wherein the molar ratio of the lithium metal powder to the lithium chloride is 2: 3, uniformly mixing and pressing a film in a nitrogen atmosphere, then sintering in the nitrogen under pressurization, crushing until the median D50 of the particle size is 15 micrometers, preparing a lithium removal material, repeating the step for 4 times to form the lithium removal material 4, and taking the lithium removal material 4 as a lithium ion battery prepared by taking the lithium removal material 3 as a positive electrode material, wherein the difference of the first lithium removal capacity value of the lithium ion battery is 3mAh/g under the condition that the charging voltage is 3-4.5V; wherein the total lithium content in the added mixture of the metal lithium powder and the lithium chloride is higher than the molar percentage of the lithium content in the finally prepared delithiation material by 0.1 percent, the sintering processes are all set multistage sintering, the temperature is kept for T1 at a rapid temperature rise speed V1-T1 temperature platform, then the temperature is kept for T2 at a rapid temperature drop speed V2-T2 temperature platform, the pressure of sintering pressurization is 30bar, V1 is 15 ℃/min, T1 is 800 ℃, and T1 is 60min, V2 is 15 ℃/min, T2 is 400 ℃, and T2 is 6 h; the chemical formula of the lithium removing material is Li(9x+2y+z)MnyMezO(3y+z)N2xX3x(xLi9N2X3·yLi2MnO3zA) where x is 0.05, y is 0.25, z is 0.7, Me is Fe and Ni, A is Li2NiO2And Li5FeO4And X is Cl.
Example 2
The same preparation as in example 1, except that the metal salt chosen was analytically pure Li2NiO2And analytically pure Li5FeO4In which Li2NiO2：Li5FeO4In a molar ratio of 4: 1; the lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 3.5 mAh/g; in the delithiation 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 chosen was analytically pure Li2NiO2And analytically pure Li5FeO4In which Li2NiO2：Li5FeO4In a molar ratio of 3: 2; the lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 3.6 mAh/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 chosen was analytically pure Li2NiO2(ii) a The lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 4.3 mAh/g; in the delithiated material, x is0.15, y is 0.35, z is 0.5, Me is Ni, A is Li2NiO2。
Example 5
The same preparation as in example 1, except that the metal salt chosen was analytically pure Li2NiO2And analytically pure Li5FeO4In which Li2NiO2：Li5FeO4In a molar ratio of 2: 3; the lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 4 mAh/g; in the delithiation material, x is 0.2, y is 0.15, and z is 0.65.
Example 6
The same preparation as in example 1, except that the metal salt chosen was analytically pure Li5FeO4B, carrying out the following steps of; the lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 3.9 mAh/g; in the delithiation material, x is 0.2, y is 0.25, z is 0.55, Me is Fe, A is Li5FeO。
Example 7
The same preparation method as in example 1 except that the heat treatment condition was heating at 600 ℃ for 20 hours; adding a mixture of equivalent lithium metal powder and lithium bromide into the crushed precursor, wherein the molar ratio of the lithium metal powder to the lithium bromide is 2.5: 3; the lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 3.8 mAh/g; the pressure for sintering and pressurizing is 40bar, V1 is 15 ℃/min, T1 is 700 ℃, T1 is 90min, V2 is 15 ℃/min, T2 is 450 ℃, T2 is 6 h; in the delithiation material, X is Br.
Example 8
The same preparation method as in example 1 except that the heat treatment condition was heating at 600 ℃ for 20 hours; adding a mixture of equivalent lithium metal powder and lithium iodide into the crushed precursor, wherein the molar ratio of the lithium metal powder to the lithium iodide is 2.5: 3; the lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 2.5 mAh/g; the total lithium content in the metal lithium powder and the lithium iodide is higher than the molar percentage of the lithium content in the lithium removing material by 0.5 percent; the lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 4.5 mAh/g; the pressure for sintering and pressurizing is 50bar, V1 is 15 ℃/min, T1 is 750 ℃, T1 is 90min, V2 is 15 ℃/min, T2 is 550 ℃, T2 is 7 h; in the delithiation material, X is I.
Example 9
The same preparation as in example 1, except that the metal salt chosen was analytically pure Li2NiO2(ii) a Adding a mixture of equal amounts 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 2.5: 3; the lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 4.6 mAh/g; the total lithium content in the metal lithium powder and the lithium iodide is higher than 0.3 percent of the molar percentage of the lithium content in the lithium removing material; the pressure for sintering and pressurizing is 30bar, V1 is 15 ℃/min, T1 is 750 ℃, T1 is 60min, V2 is 15 ℃/min, T2 is 500 ℃, T2 is 5 h; in the delithiation material, x is 0.05, y is 0.25, z is 0.7, Me is Ni, A is Li2NiO2。
Example 10
The same preparation as in example 9, except that the metal salt chosen was analytically pure Li2NiO2And analytically pure Li5FeO4In which Li2NiO2：Li5FeO4In a molar ratio of 4: 1; repeating for 4 timesCompared with a lithium ion battery prepared by taking the lithium removing material 3 formed after repeating the lithium removing material 4 for 3 times as a positive electrode material, the lithium ion battery has the first lithium removing capacity value difference of 4.7mAh/g under the condition that the charging voltage is 3-4.5V; in the delithiation 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 chosen was analytically pure Li2NiO2And analytically pure Li5FeO4In which Li2NiO2：Li5FeO4In a molar ratio of 3: 2; in the delithiation material, x is 0.1, y is 0.25, z is 0.65, and A is Li2NiO2And Li5FeO4。
Example 12
The same preparation as in example 9, except that the metal salt chosen was analytically pure Li2NiO2And analytically pure Li5FeO4In which Li2NiO2：Li5FeO4The molar ratio is 1: 1; the lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 4.5 mAh/g; in the delithiation 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 chosen was analytically pure Li2NiO2And analytically pure Li5FeO4In which Li2NiO2：Li5FeO4In a molar ratio of 2: 3; the lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 3.8 mAh/g; in the delithiation material, x is 0.2, y is 0.15, and z is 0.65.
Example 14
And embodiments thereof9 the same preparation method, except that the metal salt is selected as analytically pure Li5FeO4A mixture of (a); the lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 3.7 mAh/g; in the delithiation material, x is 0.2, y is 0.25, z is 0.55, Me is Fe, A is Li5FeO4。
Example 15
The same preparation method as in example 1 except that the heat treatment condition was heating at 800 ℃ for 30 hours; adding equal amounts of 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; the lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 3.5 mAh/g; the total lithium content in the metal lithium powder and the lithium fluoride is higher than 0.5 percent of the molar percentage of the lithium content in the lithium removing material; the pressure for sintering and pressurizing is 100bar, V1 is 15 ℃/min, T1 is 900 ℃, T1 is 100min, V2 is 15 ℃/min, T2 is 500 ℃, T2 is 8 h; in the delithiation material, X is F.
Example 16
The same preparation as in example 1, except that the metal salt chosen was analytically pure Li6CoO4And analytically pure Li6MnO4In which Li6CoO4：Li6MnO4In a molar ratio of 1: 1; the heat treatment condition is heating for 30 hours at 700 ℃; adding equal amounts 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; the lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 4.1 mAh/g; the total lithium content in the metal lithium powder and the lithium chloride is higher than 0.5 percent of the molar percentage of the lithium content in the lithium removing material; the pressure of sintering pressurization is 100bar, V1 ═ 15 ℃/min, T1 ═ 900 ℃, T1 ═ 100min, V2 ═ 15 ℃/min, T2 ═ 500 ℃, T2 ═ 8 h; in the delithiation material, Me is Co, and A is Li6CoO4And Li6MnO4。
Comparative example 1
10kg of metal salt was taken as analytically pure Li2NiO2(ii) a Taking 1kg of analytically pure manganese sulfate; mixing Li2NiO2Preparing 1mol/L sulfate solution with manganese sulfate as a raw material, adding 5L sulfate solution, 8L 1mol/L sodium hydroxide solution and 0.2L 10mol/L ammonia water into a reaction container to react, filtering, washing and drying the precipitate to prepare a precursor, and then carrying out heat treatment and crushing under the nitrogen atmosphere, wherein the heat treatment condition is heating at 600 ℃ for 30 hours; crushing until the median D50 of the particle size of the precursor is 15 μm; adding a mixture of equal amounts 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 2: 3, uniformly mixing in a nitrogen atmosphere, pressing a film, sintering in nitrogen under pressure to prepare a sintering material 1, and crushing until the median D50 of the particle size is 15 microns; and repeating the steps for 4 times, and adding 100g of a mixture of lithium metal powder and lithium chloride into the crushed sintering material 1, wherein the molar ratio of the lithium metal powder to the lithium chloride is 2: 3, uniformly mixing and pressing a film in a nitrogen atmosphere, then sintering in the nitrogen under pressurization, crushing until the median D50 of the particle size is 15 micrometers, and preparing a lithium removal material, wherein the lithium removal material 4 formed after repeating for 4 times is more than the lithium removal material 3 formed after repeating for 3 times and is used as a lithium ion battery prepared by using the anode material, and under the condition that the charging voltage is 3-4.5V, the first lithium removal capacity value difference of the lithium ion battery is 25mAh/g, wherein the total lithium content in the added mixture of the metal lithium powder and the lithium chloride is higher than the molar percentage of the lithium content in the finally prepared lithium removal material by 0.2%; the sintering process does not set a multi-section sintering platform, the temperature platform is kept for the time T1 at the rapid temperature rise speed V1-T1, the sintering and pressurizing pressure is 30bar, V1 is 15 ℃/min, T1 is 800 ℃, and T1 is 12 h; the chemical formula of the lithium removing material is Li(9x+2y+z)MnyMezO(3y+z)N2xX3x(xLi9N2X3·yLi2MnO3zA) where x is 0.05, y is 0.25, z is 0.7, Me is Ni, A is Li2NiO2And X is Cl.
Comparative example 2
The same preparation as in comparative example 1, except that the metal salt was selected as analytically pure Li2NiO2And analyzing your Li5FeO4Mixture of Li2NiO2：Li5FeO4In a molar ratio of 4: 1; the lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 21 mAh/g; in the delithiation material, x is 0.05, y is 0.35, z is 0.6, Me is Ni and Fe, A is Li2NiO2And Li5FeO4。
Comparative example 3
The same preparation as in comparative example 1, except that the metal salt was selected as analytically pure Li2NiO2And analyzing your Li5FeO4Mixture of Li2NiO2：Li5FeO4In a molar ratio of 3: 2; under the condition that the charging voltage is 3-4.5V, the lithium ion battery prepared by taking the lithium removing material 4 formed after repeating for 4 times as the anode material as the lithium removing material 3 formed after repeating for 3 times has the difference of the first lithium removing capacity value of 18mAh/g, wherein x is 0.1, y is 0.25, z is 0.65, Me is Ni and Fe, A is Li2NiO2And Li5FeO4。
Comparative example 4
The same preparation as in comparative example 1, except that Li was used as the metal salt5FeO4(ii) a Under the condition that the charging voltage is 3-4.5V, the lithium ion battery prepared by taking the lithium removing material 4 formed after repeating for 4 times as the anode material and the lithium removing material 3 formed after repeating for 3 times as the anode material has the difference of the first lithium removing capacity value of 29mAh/g, wherein x is 0.2, and y is0.25, z is 0.55, Me is Fe, A is Li5FeO4。
Comparative example 5
The same preparation method as in comparative example 1 except that the heat treatment condition was heating at 800 ℃ for 30 hours; adding a mixture of equivalent lithium metal powder and lithium chloride into the crushed precursor, wherein the molar ratio of the lithium metal powder to the lithium chloride is 3: 3; the lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 26 mAh/g; wherein the metal lithium powder also contains lithium carbonate and lithium hydroxide powder; the total lithium content in the metal lithium powder and the lithium chloride is higher than 0.5 percent of the molar percentage of the lithium content in the lithium removing material; and (3) setting a multi-stage sintering platform, wherein sintering processes are respectively sintering pressure of 30bar, T1 is 900 ℃, T2 is 500 ℃, T1 is 100min, and T2 is 8h, and repeating the sintering process for 4 times.
Comparative example 6
The same preparation method 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; the lithium removal material 4 formed after repeating for 4 times is compared with the lithium removal material 3 formed after repeating for 3 times and used as a lithium ion battery prepared from the anode material, and under the condition that the charging voltage is 3-4.5V, the difference of the lithium removal capacity values of the lithium ion battery for the first time is 31 mAh/g; wherein the metal lithium powder also contains lithium carbonate and lithium hydroxide powder; the total lithium content in the metal lithium powder and the lithium chloride is higher than 0.5 percent of the molar percentage of the lithium content in the lithium removing material; and (2) setting a multi-stage sintering platform, wherein sintering processes are all sintering pressure of 30bar, T1 is 900 ℃, T2 is 500 ℃, T1 is 100min, and T2 is 8h, and repeating the sintering process for 4 times to remove lithium in the material, wherein x is 0.2, y is 0.3, and z is 0.5.
In the embodiment or the comparative example, the sample is used as a lithium battery positive electrode material, graphite is used as a lithium battery negative electrode material, and an ethyl carbonate solution of lithium hexafluorophosphate is used as an electrolyte to jointly prepare the lithium ion battery, and the 3-4.5V first-time charging capacity of the battery is determined according to YS/T798-2012 lithium nickel cobalt manganese oxide.
The first charge capacity of the non-stored sample was subtracted from the first charge capacity of the sample stored at dew point-50 ℃ for 5 days and at a relative humidity of 10% for 10 hours, respectively, to obtain the capacity loss of the sample at dew point-50 ℃ for 5 days of dry storage and at a relative humidity of 10% for 10 hours.
The lithium ion batteries tested by the samples of examples 1-14 and comparative examples 1-4 as positive electrode materials under the condition of charging voltage of 3-4.5V have first delithiation capacity and capacity loss under the conditions of dew point-50 ℃ dry storage for 5 days and relative humidity of 10% storage for 10h, and the test results of the related examples and comparative examples are shown in Table 1
TABLE 1 first delithiation Capacity and Capacity loss test results
As can be seen from table 1, in the lithium ion batteries prepared by the lithium removal materials prepared in the invention in the embodiments 1 to 6 and 9 to 14, the first lithium removal capacity exceeds 400mAh/g, and the best performance can reach 631 mAh/g; compared with the comparative examples 1-4, the first lithium removal capacity can only reach 350 mAh/g; therefore, the lithium removing material has the advantage of high lithium removing capacity. Meanwhile, through testing the capacity loss under the conditions of dry storage for 5 days at the dew point of-50 ℃ and storage for 10 hours at the relative humidity of 10%, the capacity loss of examples 1-6 and examples 9-14 is far lower than that of comparative examples 1-4, and the practice proves that the delithiation material has excellent performance of stable performance and easy storage.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (16)
1. A delithiation material, characterized in that, said delithiation material chemical formula is: li(9x+2y+z)MnyMezO(3y+z)N2xX3x(xLi9N2X3·yLi2MnO3zA), where x is greater than 0 and less than or equal to 0.25, y is greater than 0 and less than or equal to 0.5, z is greater than or equal to 0.5 and less than or equal to 1, Me is Fe, Ni or Co, A contains Li5FeO4、Li2NiO2、Li6CoO4And Li6MnO4And X is a group viia element.
2. The delithiation material of claim 1, wherein x, y, and z are each integer multiples of 0.05.
3. The delithiation material of claim 1, wherein X is one or more of F, Cl, Br, and I.
4. A method for 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;
s2, adding the dispersed precursor in S1 into lithium metal powder and lithium halide, uniformly mixing in a nitrogen atmosphere, pressing a film, and sintering in nitrogen under pressure to prepare a sintering material 1;
s3, crushing the sintering material 1 in the S2;
s4 repeating the steps S2 and S3K 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 metal salt comprises Li5FeO4、Li2NiO2、Li6CoO4And Li6MnO4One or more of (a).
6. The method of claim 4, wherein the manganese compound comprises manganese sulfate, manganese nitrate, manganese chloride, or manganese bromide.
7. The method according to claim 4, wherein the heat treatment in S1 is carried out at a temperature of 300-900 ℃ for 10-50 h.
8. The method according to claim 7, wherein the heat treatment in S1 is performed at a temperature of 500-800 ℃ for 20-40 h.
9. The method according to claim 4, wherein the total content of free water and crystal water in the heat-treated precursor in S1 is controlled to be within 0.001% by weight.
10. The method according to claim 4, wherein the ratio of the metal lithium powder to the lithium halide is 2: 3 to 5: 3.
11. the method of claim 10, wherein the ratio of the metal lithium powder to the lithium halide is 2: 3 to 3: 3.
12. the method of claim 4, wherein the total lithium content of the lithium metal powder and the lithium halide is 0.01 to 10% higher than the lithium content of the delithiation material in terms of mole percent.
13. The method of claim 12, wherein the total lithium content of the lithium metal powder and the lithium halide is 0.1 to 5% higher than the lithium content of the delithiated material, in terms of mole percent.
14. The method of claim 4, wherein the sintering pressures in S2 and S4 are 10bar to 100 bar.
15. The method as claimed in claim 4, wherein the sintering is a multi-stage sintering, the temperature is raised to T1 at a temperature raising speed of V1 and kept for a temperature platform keeping time of T1, then the temperature is lowered to T2 at a temperature lowering speed of V2 and kept for a temperature platform keeping time of T2, the temperature raising speed of V1 and the temperature lowering speed of V2 are not lower than 10 ℃/min, T1 is not lower than 700 ℃ and not higher than 950 ℃, T2 is not lower than 300 ℃ and not higher than 500 ℃, T1 is not lower than 30min and not higher than 120min, and T2 is not lower than 5h and not higher than 8 h.
16. The method according to claim 4, wherein the difference between the first delithiation capacity value of the lithium ion battery prepared by using the delithiation material K formed after repeating the steps of K times of S2 and S3 as a positive electrode material is less than 5mAh/g compared with the lithium ion battery prepared by using the delithiation material K-1 formed after repeating the steps of K-1 times of S2 and S3 as a positive electrode material under the condition that the charging voltage is 3-4.5V.
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| CN113353991B (en) | 2023-06-30 |
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