CN111430702B - Doped anode material and preparation method and application thereof - Google Patents
Doped anode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a doped anode material and a preparation method and application thereof. The doped anode material comprises: the cathode material comprises a cathode material body and a doping material, wherein the doping material is distributed in the cathode material body, and the concentration of the doping material is gradually reduced along the direction from the inside to the surface of the cathode material body. The doped anode material is modified by the doped material, so that the overall electrochemical performance is remarkably improved, and the doped material is gradually reduced in concentration along the direction from the inside of the anode material body to the surface, so that the doped anode material has higher structural stability, greatly reduces the side reaction activity when contacting with an electrolyte, and is suitable for application of the anode material of an all-solid-state battery. In addition, by adopting the doping modification, the characteristics of solid-solid phase contact and phase interface between the anode material and the electrolyte can be obviously improved, the cycle capacity of the battery is improved, and the rate capability under large current is improved.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a doped anode material and a preparation method and application thereof.
Background
The all-solid-state battery is considered as the next generation of energy storage power supply with great potential, and the reason is that the battery has the characteristics of high safety, high energy density and the like. For all-solid batteries, there are still a number of problems to be solved, such as poor solid-state electrolyte conductivity, electrode/electrolyte solid-solid interface contact and side reactions, lithium negative lithium dendrites, etc. The interface problem is particularly important and deserves much attention and research. In the process of charging and discharging, the positive electrode material causes the shrinkage and expansion of a crystal structure due to the insertion and extraction of lithium ions, and the solid-solid interface between the positive electrode material and the electrolyte is damaged due to the volume change; on the other hand, the lithium ion diffusion rate is hindered by a product generated by a chemical reaction between the cathode material and the electrolyte.
Solid electrolytes are generally considered to have the following advantages: (1) is non-volatile and difficult to burn; (2) the wide electrochemical window can be matched with a high-voltage anode material; (3) the energy density of the battery is improved. Solid-state electrolytes are generally classified into the following categories: oxide electrolytes, sulfide electrolytes, polymer electrolytes, and the like. The sulfide electrolyte is a solid electrolyte with high conductivity and sulfur replaces oxygen. Another advantage of sulfide electrolytes is their good mechanical properties. The material shows plastic deformation characteristic under mechanical pressure, and can form a compact interface with a positive electrode material. In recent years, the research focus of solid sulfide electrolytes is based on the LPSCl system, which has relatively low synthesis process difficulty, high ionic conductivity, stable chemical state and good mechanical properties. Due to the lithium ion potential difference between the positive electrode material and the solid sulfide electrolyte, lithium ions can migrate from the electrolyte to the positive electrode, thereby forming Surface Charge Layers (SCLs) on both sides of the positive electrode and the electrolyte. This surface charge layer is one of the important causes of polarization. The introduction of a buffer layer is an effective strategy to avoid the formation of surface charge layers. With LiNbO 3 Coating the positive electrode material is one of the most successful methods at present. However, due to LiNbO 3 The ion conductivity of the coating material is low, and the coating material layer can generally cause the specific discharge capacity to be reduced at a higher current multiplying factor. Especially high nickel ternary positive electrode material LiNbO 3 The problem of the coating is more obvious. In summary, the conventional solid state power deviceCells and electrode materials suitable for solid-state batteries remain to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a doped cathode material, a preparation method and application thereof. The doped anode material has higher structural stability by adopting gradient cation doping, and the side reaction activity is greatly reduced when the doped anode material is in contact with an electrolyte.
In one aspect of the invention, a doped positive electrode material is provided. According to an embodiment of the invention, the doped positive electrode material comprises: a body of positive electrode material; the doping material is distributed in the positive electrode material body, and the concentration of the doping material is gradually reduced along the direction from the inside to the surface of the positive electrode material body.
According to the doped cathode material provided by the embodiment of the invention, through modification of the doped material, on one hand, the whole electrochemical performance is obviously improved, on the other hand, through adopting a gradient design that the concentration of the doped material is gradually reduced along the direction from the inside to the surface of the cathode material body, higher structural stability is obtained, and the side reaction activity is greatly reduced when the doped cathode material is in contact with an electrolyte, so that the doped cathode material is suitable for application of all-solid-state battery cathode materials. In addition, by adopting the doping modification, the characteristics of solid-solid phase contact and phase interface between the anode material and the electrolyte can be obviously improved, the cycle capacity of the battery is improved, and the rate capability under large current is improved.
In addition, the doped positive electrode material according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the body of positive electrode material comprises at least one selected from the group consisting of an oxide, a sulfide, and a selenide.
In some embodiments of the present invention, the positive electrode material body includes at least one selected from lithium nickel manganese oxide, lithium cobalt oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide, vanadium pentoxide, lithium cobalt manganese oxide, lithium sulfide, and vanadium sulfide.
In some embodiments of the invention, the doping material comprises at least one selected from the group consisting of Ti, V, nb, ge, mg, al, zr, zn, cr, la, ce.
In some embodiments of the invention, the concentration of the dopant material is from 500ppm to 8000ppm.
In another aspect of the present invention, the present invention provides a method for preparing the doped positive electrode material of the above embodiment. According to an embodiment of the invention, the method comprises: (1) Adding a metal salt solution, a doping element precursor solution, a precipitator and a complexing agent into the reaction base solution, and reacting to obtain mixed slurry; (2) Carrying out post-treatment on the mixed slurry to obtain a doped anode material precursor; (3) Mixing the doped anode material precursor with a lithium source and calcining to obtain the doped anode material; in the process of adding the doping element precursor liquid into the reaction base liquid, the unit time adding amount of the doping element precursor liquid and the reaction proceeding time meet the decreasing linear function relationship or the decreasing exponential function relationship. Therefore, the doped anode material doped with the gradient concentration can be simply, conveniently and efficiently prepared, and the preparation method is low in cost and easy for large-scale production.
In addition, the method for preparing the doped cathode material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, during the process of adding the doping element precursor solution to the reaction base solution, the addition amount per unit time of the doping element precursor solution and the reaction proceeding time satisfy a functional relationship shown in formula (I) or formula (II):
y＝mx+b (I)
y＝n x (II)
in the formulas (I) and (II), y is the unit time adding amount of the mixed element precursor solution, x is the time for carrying out the reaction, and-10-type woven-fabric-type (m) woven-fabric-type (0), and-5-b-5, 0-type woven-fabric-type (n) woven-fabric-type (1).
In some embodiments of the present invention, the concentration of the doping element precursor solution is 5 to 80g/L.
In some embodiments of the invention, the metal salt solution has a concentration of 60 to 160g/L.
In some embodiments of the invention, the precipitating agent is an aqueous sodium hydroxide solution.
In some embodiments of the invention, the complexing agent is an aqueous ammonia solution.
In yet another aspect of the present invention, a battery is provided. According to an embodiment of the present invention, the battery includes: a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises the doped positive electrode material of the embodiment. Thus, the cell has all the features and advantages described above for the doped positive electrode material, which are not described in detail here. In general, the battery has excellent electrochemical properties such as energy density, rate capability, cycle performance and the like.
In addition, the battery according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the electrolyte comprises Li 7 P 3 S 11 、Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 、Li 10 SnP 2 S 12 、Li 6 PS 5 Cl、Li 3 PS 4 、Li 2 S–P 2 S 5 、75Li 2 S·25P 2 S 5 、90Li 3 PS 4 –10ZnO、9Li 2 S-3P 2 S 5 -1Ni 3 S 2 、60Li 2 S-25P 2 S 5 –10Li 3 N、78Li 2 S-22P 2 S 5 、80(0.7Li 2 S-0.3P 2 S5)-20LiI、99(70Li 2 S-30P 2 S 5 )-1Li 2 ZrO 3 、70Li 2 S-29P 2 S 5 -1Li 3 PO 4 、70Li 2 S-29P 2 S 5 -1P 2 S 3 、Li 7 P 2.9 S 10.85 Mo 0.01 、90(0.7Li 2 S-0.3P 2 S 5 )-10LiBr、75Li 2 S-23P 2 S 5 -2P 2 Se 5 、95(0.8Li 2 S-0.2P 2 S 5 )-5LiI、Li 10.35 [Sn 0.27 Si 1.08 ]P 1.65 S 12 、Li 10 GeP 2 S 12 、Li 11 AlP 2 S 12 At least one of (a).
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic illustration of a dopant element concentration profile in a doped positive electrode material according to one embodiment of the present invention;
FIG. 2 is an SEM morphology of the cathode material prepared in example 4 and elemental analysis thereof;
fig. 3 is a first charge-discharge curve of the all-solid battery at 0.1C rate in example 7;
fig. 4 is a discharge specific capacity change curve of the all-solid battery of example 7 for 50 cycles;
fig. 5 is a comparison of the performance of cells made with different doping levels of the positive electrode material of example 7.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In addition, it should be noted that, in the description of the present invention, the inside of the positive electrode material body should be understood in a broad sense. In the doped cathode material of the present invention, the concentration of the doped material gradually increases in the direction from the surface to the inside of the cathode material body. For a positive electrode material body with a relatively regular shape (for example, a spherical or spheroidal particulate positive electrode material body), the term inside the positive electrode material body refers to the center or a position close to the center of the positive electrode material body, that is, in the doped positive electrode material of the present invention, the concentration of the doping material on the surface of the positive electrode material body is the lowest, and in the radial direction of the positive electrode material body, the concentration of the doping material gradually increases from the surface of the positive electrode material body to the inside.
In one aspect of the invention, a doped positive electrode material is provided. According to an embodiment of the present invention, the doped positive electrode material includes: a body of positive electrode material; the doping material is distributed in the positive electrode material body, and the concentration of the doping material is gradually reduced along the direction from the inside to the surface of the positive electrode material body.
According to the doped anode material provided by the embodiment of the invention, the overall electrochemical performance is obviously improved through the modification of the doped material, and on the other hand, higher structural stability is obtained through the gradient design that the concentration of the doped material is gradually reduced along the direction from the inside to the surface of the anode material body, and the side reaction activity is greatly reduced when the doped anode material is in contact with an electrolyte, so that the doped anode material is suitable for the application of the anode material of an all-solid battery. In addition, by adopting the doping modification, the characteristics of solid-solid phase contact and phase interface between the anode material and the electrolyte can be obviously improved, the cycle capacity of the battery is improved, and the rate capability under large current is improved.
The doped positive electrode material according to an embodiment of the present invention is further described in detail below:
according to a specific example of the present invention, the concentration profile of the doping element in the doped cathode material is shown in fig. 1. In fig. 1, on the cross section of the positive electrode material particle, the darker the color represents the higher the concentration of the doping element.
The specific type of the above-mentioned cathode material body is not particularly limited, and can be selected by those skilled in the art according to actual needs. That is, the gradient concentration doping method proposed in the present invention does not specifically limit the specific type of the positive electrode material. According to some embodiments of the present invention, the above-mentioned body of the cathode material may include at least one selected from the group consisting of an oxide, a sulfide, and a selenide. The gradient concentration doping mode provided by the invention has wide application range and can be suitable for modifying various anode materials.
According to some embodiments of the present invention, the positive electrode material body may include at least one selected from lithium nickel manganese oxide, lithium cobalt oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide, vanadium pentoxide, lithium cobalt manganese oxide, lithium sulfide, and vanadium sulfide.
According to some embodiments of the invention, the doping material may include at least one selected from Ti, V, nb, ge, mg, al, zr, zn, cr, la, ce. In some embodiments, the elements may dope the bulk of the anode material in the form of cations and/or oxides. By adopting the doping material, the stability of the anode material can be further improved, and the side reaction activity when the anode material is contacted with the electrolyte can be further reduced. The doped anode material adopting the doped material is more suitable for the application of the anode material of the all-solid-state battery.
According to some embodiments of the present invention, the concentration of the doping material may be 500ppm to 8000ppm, such as 500ppm, 1000ppm, 2000ppm, 3000ppm, 4000ppm, 5000ppm, 6000ppm, 7000ppm, 8000ppm, and the like. The doping material is distributed in a gradient concentration in the positive electrode material body, and the above concentration value refers to the overall concentration of the doping material in the positive electrode material body. The inventors have found in their studies that the performance of the positive electrode material can be further improved by controlling the concentration of the dopant material within the above range. If the concentration of the doping material is too low, the performance of the anode material is not obviously improved; if the concentration of the doped material is too high, the performance of the cathode material may be adversely affected, even lower than that of the undoped modified cathode material.
According to some embodiments of the present invention, the concentration of the doping material may be 0.005-0.08-mol, such as 0.005-0.01-0.02-0.03-0.04-0.05-0, 0.06-0.07-0.08-0, etc. The doping material is distributed in a gradient concentration in the positive electrode material body, and the above concentration value refers to the overall concentration of the doping material in the positive electrode material body. The inventors have found in their studies that the performance of the positive electrode material can be further improved by controlling the concentration of the dopant material within the above range. If the concentration of the doped material is too low, the performance of the anode material is not obviously improved; if the concentration of the doped material is too high, the performance of the cathode material may be adversely affected, even lower than that of the undoped modified cathode material.
In another aspect of the invention, the invention provides a method of preparing the doped positive electrode material of the above embodiment. According to an embodiment of the invention, the method comprises: (1) Adding a metal salt solution, a doping element precursor solution, a precipitator and a complexing agent into the reaction base solution, and reacting to obtain mixed slurry; (2) Carrying out post-treatment on the mixed slurry to obtain a doped anode material precursor; (3) Mixing the doped anode material precursor with a lithium source and calcining to obtain a doped anode material; in the process of adding the doping element precursor liquid into the reaction base liquid, the unit time adding amount of the doping element precursor liquid and the reaction proceeding time meet the decreasing linear function relationship or the decreasing exponential function relationship.
According to the embodiment of the invention, the method can simply, conveniently and efficiently prepare the doped anode material with the gradient concentration doping, has low cost and is easy for large-scale production by controlling the adding flow rate of the doping element precursor liquid in the process of preparing the doped anode material by a coprecipitation method.
According to some embodiments of the present invention, in the process of adding the doping element precursor solution to the reaction base solution, the addition amount per unit time of the doping element precursor solution and the reaction proceeding time satisfy a functional relationship shown in formula (I) or formula (II):
y＝mx+b (I)
y＝n x (II)
in the formulas (I) and (II), y is the unit time adding amount of the mixed element precursor solution, x is the time for carrying out the reaction, and-10-type woven-fabric-type (m) woven-fabric-type (0), and-5-b-5, 0-type woven-fabric-type (n) woven-fabric-type (1). The inventors found in the research that by controlling the addition amount per unit time of the doping element precursor solution and the reaction progress time to satisfy the above functional relationship, the gradient concentration distribution of the doping material in the positive electrode material body can be further ensured, and the performance of the positive electrode material can be further improved.
According to some embodiments of the present invention, the concentration of the doping element precursor solution may be 5 to 80g/L, such as 5g/L, 10g/L, 20g/L, 60g/L, 80g/L, and the like. Therefore, the forming of the positive electrode material particles and the gradient concentration distribution of the doping material in the positive electrode material can be further facilitated.
According to some embodiments of the present invention, the metal salt solution may have a concentration of 60 to 160g/L, such as 60g/L, 80g/L, 100g/L, 120g/L, 140g/L, 160g/L, and the like. Therefore, the forming of the positive electrode material particles and the gradient concentration distribution of the doping material in the positive electrode material can be further facilitated. In addition, when a plurality of metal salt solutions are used, the above concentration refers to the concentration of one of the metal salt solutions.
According to some embodiments of the present invention, the precipitant may be an aqueous sodium hydroxide solution, and the complexing agent may be an aqueous ammonia solution. The concentrations of the precipitant and complexing agent can be, independently, 80-240 g/L, such as 80g/L, 120g/L, 160g/L, 200g/L, 240g/L, and the like. Therefore, the forming of the positive electrode material particles and the gradient concentration distribution of the doping material in the positive electrode material can be further facilitated.
The method for preparing the doped positive electrode material is described below by taking the preparation of the titanium-doped nickel cobalt lithium manganate positive electrode material as an example.
Step 1: preparing nickel sulfate, cobalt sulfate, manganese sulfate with certain concentration (for example, 60-160 g/L), titanium sulfate solution with certain concentration (for example, 5-120 g/L), ammonia water solution with certain concentration (for example, 80-240 g/L) and sodium hydroxide solution;
step 2: adding a certain volume of deionized water into a reaction kettle, and heating the reaction kettle to a certain constant temperature (for example, 50-80 ℃);
and step 3: adjusting the stirring speed of the reaction kettle to a certain value (for example, 800-1200 rpm);
and 4, step 4: respectively injecting the prepared solution into a reaction kettle by using a peristaltic pump, wherein the flow rate of injecting the nickel sulfate, the cobalt sulfate, the manganese sulfate, the ammonia water and the sodium hydroxide aqueous solution into the reaction kettle is kept constant, and the flow rate of injecting the titanium sulfate solution into the reaction kettle is set to be in the functional relation;
and 5: monitoring and adjusting the pH value of the solution in the reaction kettle to 10-11.9 on line;
step 6: collecting samples in the kettle at regular time to test the particle size distribution;
and 7: filtering, washing with deionized water and vacuum drying (100-150 deg.C, 6-12 h);
and 8: and (3) mixing the doped positive electrode material precursor obtained by post-treatment with lithium hydroxide according to the molar ratio of 1 (1.00-1.04), fully grinding and uniformly mixing, calcining the mixture at 750 ℃ in an oxygen atmosphere or an oxygen-nitrogen mixed atmosphere for 10 hours, taking out solid powder after the calcining is finished, and grinding and sieving to obtain the titanium-doped nickel-cobalt lithium manganate positive electrode material.
In yet another aspect of the present invention, a battery is provided. According to an embodiment of the present invention, the battery includes: a positive electrode, a negative electrode and an electrolyte, the positive electrode comprising the doped positive electrode material of the above embodiment. Thus, the cell has all the features and advantages described above for the doped positive electrode material, which are not described in detail here. In general, the battery has excellent electrochemical properties such as energy density, rate capability, cycle performance and the like.
According to some embodiments of the invention, the electrolyte may include Li 7 P 3 S 11 、Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 、Li 10 SnP 2 S 12 、Li 6 PS 5 Cl、Li 3 PS 4 、Li 2 S–P 2 S 5 、75Li 2 S·25P 2 S 5 、90Li 3 PS 4 –10ZnO、9Li 2 S-3P 2 S 5 -1Ni 3 S 2 、60Li 2 S-25P 2 S 5 –10Li 3 N、78Li 2 S-22P 2 S 5 、80(0.7Li 2 S-0.3P 2 S5)-20LiI、99(70Li 2 S-30P 2 S 5 )-1Li 2 ZrO 3 、70Li 2 S-29P 2 S 5 -1Li 3 PO 4 、70Li 2 S-29P 2 S 5 -1P 2 S 3 、Li 7 P 2.9 S 10.85 Mo 0.01 、90(0.7Li 2 S-0.3P 2 S 5 )-10LiBr、75Li 2 S-23P 2 S 5 -2P 2 Se 5 、95(0.8Li 2 S-0.2P 2 S 5 )-5LiI、Li 10.35 [Sn 0.27 Si 1.08 ]P 1.65 S 12 、Li 10 GeP 2 S 12 、Li 11 AlP 2 S 12 At least one of (a). The electrolyte has better adaptability with the doped anode material provided by the invention, and the battery performance can be further improved by adopting the electrolyte.
According to some embodiments of the present invention, the negative electrode includes a negative electrode material, and the negative electrode material may be lithium metal, lithium indium alloy, graphite, silicon alloy, silicon dioxide, a mixture of silicon dioxide and graphite, or a mixture of silicon dioxide/graphite/silicon. Thereby, the battery performance can be further improved.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
Synthesizing a precursor of the anode material:
preparing 120g/L of nickel sulfate, cobalt sulfate, manganese sulfate and 5g/L of titanium sulfate solution, and preparing 200g/L of ammonia water solution and sodium hydroxide water solution. Adding a certain volume of deionized water into the reaction kettle, and heating the reaction kettle to a constant temperature of 70 ℃. The stirring speed of the reaction kettle is adjusted to 1200rpm. And respectively injecting the prepared solutions into a reaction kettle by using a peristaltic pump, respectively keeping the flow rates of the nickel sulfate solution, the cobalt sulfate solution, the manganese sulfate solution, the ammonia water and the sodium hydroxide solution into the reaction kettle at constant values, and setting the flow rate of the titanium sulfate solution into the reaction kettle as a linear function y = -0.1x. The pH in the reactor solution was monitored and adjusted to 11.3 on-line. Samples in the kettle were collected periodically to test particle size distribution. The resulting material was filtered, washed with deionized water and dried under vacuum (130 ℃,10 h). The Ti element in the precursor presents a gradually-reduced gradient distribution trend from the interior of the particle to the surface of the particle, and the total Ti content in the precursor is 0.005mol%.
Synthesizing a positive electrode material:
the precursor and lithium hydroxide were mixed in a molar ratio of 1.04. And after fully grinding and uniformly mixing, calcining the mixture at 750 ℃ in an oxygen atmosphere or an oxygen-nitrogen mixed atmosphere for 10 hours, taking out solid powder after the calcining is finished, and grinding and sieving the solid powder to obtain a doped anode material product.
Example 2
Synthesizing a precursor of the anode material:
120g/L of nickel sulfate, cobalt sulfate, manganese sulfate and 10g/L of titanium sulfate solution are prepared, and 200g/L of ammonia water solution and sodium hydroxide water solution are prepared. Adding a certain volume of deionized water into the reaction kettle, and heating the reaction kettle to a constant temperature of 70 ℃. The stirring speed of the reaction kettle is adjusted to 1200rpm. And respectively injecting the prepared solutions into a reaction kettle by using a peristaltic pump, respectively keeping the flow rates of the nickel sulfate solution, the cobalt sulfate solution, the manganese sulfate solution, the ammonia water and the sodium hydroxide solution into the reaction kettle at constant values, and setting the flow rate of the titanium sulfate solution into the reaction kettle as a linear function y = -0.1x. The pH in the kettle solution was monitored on-line and adjusted to 11.3. Samples in the kettle were collected periodically to test particle size distribution. The resulting material was filtered, washed with deionized water and dried under vacuum (130 ℃,10 h). The Ti element in the precursor presents a gradually reduced gradient distribution trend from the interior of the particle to the surface of the particle, and the total Ti content in the precursor is 0.01mol%.
And (3) synthesizing a positive electrode material:
the precursor and lithium hydroxide were mixed in a molar ratio of 1.04. And after fully grinding and uniformly mixing, calcining the mixture at 750 ℃ in an oxygen atmosphere or an oxygen-nitrogen mixed atmosphere for 10 hours, taking out solid powder after the calcining is finished, and grinding and sieving the solid powder to obtain a doped anode material product.
Example 3
Synthesizing a precursor of the anode material:
preparing 120g/L of nickel sulfate, cobalt sulfate, manganese sulfate and 20g/L of titanium sulfate solution, and preparing 200g/L of ammonia water solution and sodium hydroxide water solution. Adding a certain volume of deionized water into the reaction kettle, and heating the reaction kettle to a constant temperature of 70 ℃. The stirring speed of the reaction kettle is adjusted to 1200rpm. And respectively injecting the prepared solutions into a reaction kettle by using a peristaltic pump, respectively keeping the flow rates of the nickel sulfate solution, the cobalt sulfate solution, the manganese sulfate solution, the ammonia water and the sodium hydroxide solution into the reaction kettle at constant values, and setting the flow rate of the titanium sulfate solution into the reaction kettle as a linear function y = -0.1x. The pH in the reactor solution was monitored and adjusted to 11.3 on-line. Samples in the kettle were collected periodically to test particle size distribution. The resulting material was filtered, washed with deionized water and dried under vacuum (130 ℃,10 h). The Ti element in the precursor presents a gradually-reduced gradient distribution trend from the interior of the particle to the surface of the particle, and the total Ti content in the precursor is 0.02mol%.
And (3) synthesizing a positive electrode material:
the precursor and lithium hydroxide were mixed in a molar ratio of 1.04. And after fully grinding and uniformly mixing, calcining the mixture at 750 ℃ in an oxygen atmosphere or an oxygen-nitrogen mixed atmosphere for 10 hours, taking out solid powder after the calcining is finished, and grinding and sieving the solid powder to obtain a doped anode material product.
Example 4
Synthesizing a precursor of the anode material:
preparing 120g/L of nickel sulfate, cobalt sulfate, manganese sulfate and 30g/L of titanium sulfate solution, and preparing 200g/L of ammonia water solution and sodium hydroxide water solution. Adding a certain volume of deionized water into the reaction kettle, and heating the reaction kettle to a certain constant temperature of 70 ℃. The stirring speed of the reaction kettle is adjusted to 1200rpm. And respectively injecting the prepared solutions into a reaction kettle by using a peristaltic pump, respectively keeping the flow rates of the nickel sulfate solution, the cobalt sulfate solution, the manganese sulfate solution, the ammonia water and the sodium hydroxide solution into the reaction kettle at constant values, and setting the flow rate of the titanium sulfate solution into the reaction kettle as a linear function y = -0.1x. The pH in the reactor solution was monitored and adjusted to 11.3 on-line. Samples in the kettle were collected periodically to test particle size distribution. The resulting material was filtered, washed with deionized water and dried under vacuum (130 ℃,10 h). The Ti element in the precursor presents a gradually-reduced gradient distribution trend from the interior of the particles to the surface of the particles, and the total Ti content in the precursor is 0.03mol%.
Synthesizing a positive electrode material:
the precursor and lithium hydroxide were mixed in a molar ratio of 1.04. And after fully grinding and uniformly mixing, calcining the mixture in an oxygen atmosphere or an oxygen-nitrogen mixed atmosphere at 750 ℃ for 10 hours, taking out solid powder after the calcining is finished, and grinding and sieving the solid powder to obtain a doped anode material product.
Example 5
Synthesizing a precursor of the anode material:
120g/L of nickel sulfate, cobalt sulfate, manganese sulfate and 50g/L of titanium sulfate solution are prepared, and 200g/L of ammonia water solution and sodium hydroxide water solution are prepared. Adding a certain volume of deionized water into the reaction kettle, and heating the reaction kettle to a certain constant temperature of 70 ℃. The stirring speed of the reaction kettle is adjusted to 1200rpm. And respectively injecting the prepared solutions into a reaction kettle by using a peristaltic pump, respectively keeping the flow rates of the nickel sulfate solution, the cobalt sulfate solution, the manganese sulfate solution, the ammonia water and the sodium hydroxide solution into the reaction kettle at constant values, and setting the flow rate of the titanium sulfate solution into the reaction kettle as a linear function y = -0.1x. The pH in the kettle solution was monitored on-line and adjusted to 11.3. Samples in the kettle were collected periodically to test particle size distribution. The resulting material was filtered, washed with deionized water and dried under vacuum (130 ℃,10 h). The Ti element in the precursor presents a gradually-reduced gradient distribution trend from the interior of the particle to the surface of the particle, and the total Ti content in the precursor is 0.05mol%.
Synthesizing a positive electrode material:
the precursor and lithium hydroxide were mixed in a molar ratio of 1.04. And after fully grinding and uniformly mixing, calcining the mixture at 750 ℃ in an oxygen atmosphere or an oxygen-nitrogen mixed atmosphere for 10 hours, taking out solid powder after the calcining is finished, and grinding and sieving the solid powder to obtain a doped anode material product.
Example 6
Synthesizing a precursor of the anode material:
120g/L of nickel sulfate, cobalt sulfate and manganese sulfate and 100g/L of titanium sulfate solution are prepared, and 200g/L of ammonia water solution and sodium hydroxide water solution are prepared. Adding a certain volume of deionized water into the reaction kettle, and heating the reaction kettle to a certain constant temperature of 70 ℃. The stirring speed of the reaction kettle is adjusted to 1200rpm. And respectively injecting the prepared solutions into a reaction kettle by using a peristaltic pump, respectively keeping the flow rates of the nickel sulfate solution, the cobalt sulfate solution, the manganese sulfate solution, the ammonia water and the sodium hydroxide solution into the reaction kettle at constant values, and setting the flow rate of the titanium sulfate solution into the reaction kettle as a linear function y = -0.1x. The pH in the reactor solution was monitored and adjusted to 11.3 on-line. Samples in the kettle were collected periodically to test particle size distribution. The resulting material was filtered, washed with deionized water and dried under vacuum (130 ℃,10 h). The Ti element in the precursor presents a gradually-reduced gradient distribution trend from the interior of the particle to the surface of the particle, and the total Ti content in the precursor is 0.1mol%.
Synthesizing a positive electrode material:
the precursor and lithium hydroxide were mixed in a molar ratio of 1.04. And after fully grinding and uniformly mixing, calcining the mixture in an oxygen atmosphere or an oxygen-nitrogen mixed atmosphere at 750 ℃ for 10 hours, taking out solid powder after the calcining is finished, and grinding and sieving the solid powder to obtain a doped anode material product.
Example 7
All solid state cell electrochemical evaluation
An all-solid-state battery was fabricated using the doped positive electrode material (designated as Ti-modified NCM-811) and the unmodified NCM-811 prepared in example 4 as the positive electrode materials, respectively, according to the following specific preparation methods:
preparing an all-solid-state sulfide battery by adopting a die battery, weighing 7mg of positive electrode material, 2.5mg of LPSCl and 0.5mg of vapor-phase grown carbon fiber, mixing and grinding in an agate mortar for 0.5-6 h. After thorough grinding and homogeneous mixing, the mixture was transferred to a die cell with a diameter of 10mm and pressed into tablets with a pressure of 70 bar. 100mg of LPSCl were then added to the mould cell and pressed again at 7bar pressure to form a solid electrolyte sheet layer. And finally, placing the lithium indium negative plate on the electrolyte, pressing all components at a pressure of 70bar, and finishing the assembly of the all-solid-state battery.
As can be seen from fig. 2, the Ti on the surface of the positive electrode material particles is uniformly distributed, which indicates that the method for optimizing the positive electrode material according to the present invention can obtain the expected element modification effect.
As can be seen from FIG. 3, for the unmodified NCM-811 material, the first charge-discharge specific capacities at 0.1C rate were 243mA · h/g and 201mA · h/g, respectively, and the first coulombic efficiency was 82.7%; the first charge-discharge specific capacity of the NCM-811 material modified by Ti is 238 mA.h/g and 207 mA.h/g respectively at 0.1C, and the first coulombic efficiency is 87%. After Ti modification, the NCM-811 cathode material can exert better discharge capacity and first coulombic efficiency.
As can be seen from FIG. 4, for the unmodified NCM-811 cathode material, the specific discharge capacity is reduced from 138mA · h/g to 100mA · h/g in the process of 50 charge-discharge cycles, and the capacity retention rate is 72.4%; for the NCM-811 cathode material modified by Ti, the specific discharge capacity is reduced from 171 mA.h/g to 129 mA.h/g in the process of 50 charge-discharge cycles, and the capacity retention rate is 75.4%. Obviously, the cycle capacity retention rate of the NCM-811 material modified by Ti is improved to some extent. The difference in specific discharge capacity between the two for each charge-discharge cycle illustrates another problem, namely that Ti can increase the lithium ion conductivity of the solid-solid interface between the positive electrode material and the electrolyte, promoting the ability of rapid migration of lithium ions under high current conditions.
As can be seen from fig. 5, the test results of the all-solid-state battery give the influence results of different Ti addition amounts: from 500ppm to 3000ppm, the corresponding first discharge specific capacity and first coulombic efficiency with 0.1C multiplying power are higher than that of unmodified (No) NCM-811, and a Ti modified sample with 3000ppm content has the highest discharge specific capacity, and the discharge specific capacities of 5000ppm and 10000ppm and the first coulombic efficiency are obviously reduced, which indicates that the effect is better when Ti modification is not added with more quantity; from 500ppm to 5000ppm, the corresponding 1C rate discharge specific capacity is higher than that of the unmodified NCM-811, and 10000ppm Ti doping causes the 1C rate performance to be reduced and is lower than that of the unmodified NCM-811.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (8)
1. A method of making a doped positive electrode material, comprising:
(1) Adding a metal salt solution, a doping element precursor solution, a precipitator and a complexing agent into the reaction base solution, and reacting to obtain mixed slurry;
(2) Carrying out post-treatment on the mixed slurry to obtain a doped anode material precursor;
(3) Mixing the doped anode material precursor with a lithium source and calcining to obtain the doped anode material;
the doped positive electrode material comprises:
a body of positive electrode material;
a dopant material distributed within the body of positive electrode material and having a concentration that gradually decreases in a direction from the interior to the surface of the body of positive electrode material,
the doping material comprises at least one of Ti, V, nb, ge, mg, al, zr, zn, cr, la and Ce, the concentration of the doping material is 500 ppm-8000 ppm,
wherein, in the process of adding the doping element precursor liquid into the reaction base liquid, the unit time adding amount of the doping element precursor liquid and the reaction proceeding time satisfy the functional relation shown in the formula (I) or the formula (II):
y＝mx+b(I)
y＝n x (II)
in the formulas (I) and (II), y is the unit time adding amount of the mixed element precursor solution, x is the time for carrying out the reaction, and-10-n-type yarn-woven fabrics are-10-5-b-5-0,
in the step (1), the metal salt solution, the doping element precursor solution, the precipitant and the complexing agent are respectively added into the reaction base solution by a peristaltic pump, the flow rates of the metal salt solution, the precipitant and the complexing agent injected into the reaction base solution are kept constant, and the flow rate of the doping element precursor solution injected into the reaction base solution is set to be in a functional relation of the formula (I) or the formula (II),
the concentration of the doping element precursor liquid is 5-80 g/L.
2. The method of claim 1, wherein the metal salt solution has a concentration of 60 to 160g/L.
3. The method of claim 1, wherein the precipitating agent is an aqueous sodium hydroxide solution.
4. The method of claim 1, wherein the complexing agent is an aqueous ammonia solution.
5. The method of claim 1, wherein the body of positive electrode material includes at least one selected from the group consisting of an oxide, a sulfide, and a selenide.
6. The method of claim 5, wherein the body of positive electrode material includes at least one selected from the group consisting of lithium nickel manganese oxide, lithium cobalt oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganate, vanadium pentoxide, lithium cobalt manganese oxide, lithium sulfide, and vanadium sulfide.
7. A battery, comprising: a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises a doped positive electrode material prepared by the method of any one of claims 1 to 6.
8. The battery of claim 7, wherein the electrolyte comprises Li 7 P 3 S 11 、Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 、Li 10 SnP 2 S 12 、Li 6 PS 5 Cl、Li 3 PS 4 、Li 2 S–P 2 S 5 、75Li 2 S·25P 2 S 5 、90Li 3 PS 4 –10ZnO、9Li 2 S-3P 2 S 5 -1Ni 3 S 2 、60Li 2 S-25P 2 S 5 –10Li 3 N、78Li 2 S-22P 2 S 5 、80(0.7Li 2 S-0.3P 2 S5)-20LiI、99(70Li 2 S-30P 2 S 5 )-1Li 2 ZrO 3 、70Li 2 S-29P 2 S 5 -1Li 3 PO 4 、70Li 2 S-29P 2 S 5 -1P 2 S 3 、Li 7 P 2.9 S 10.85 Mo 0.01 、90(0.7Li 2 S-0.3P 2 S 5 )-10LiBr、75Li 2 S-23P 2 S 5 -2P 2 Se 5 、95(0.8Li 2 S-0.2P 2 S 5 )-5LiI、Li 10.35 [Sn 0.27 Si 1.08 ]P 1.65 S 12 、Li 10 GeP 2 S 12 、Li 11 AlP 2 S 12 At least one of (a).
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