Patent Application
20250070159
The present application relates to an electrode sheet material, and in particular to a positive electrode active material and its use, belonging to the technical field of secondary batteries.
With the development and advancement of lithium-ion battery technology, there are higher capacity requirements on battery capacity. In the composition of lithium-ion batteries, the capacity of positive electrode active materials plays a vital role in the capacity of lithium-ion batteries.
In order to increase the capacity of lithium-ion batteries, the most commonly used method is to increase their charge and discharge voltage. However, as the voltage increases, the crystal structure of the positive electrode active material will collapse, leading to a series of problems such as rapid capacity decay and significantly reduced cycle performance of the battery.
Therefore, developing a positive electrode active material for lithium-ion batteries with high specific capacity and good cycle performance is a technical problem to be solved urgently in this field.
The present application provides a positive electrode active material, the special composition and crystal phase structure of the positive electrode active material are helpful to improve the specific capacity and cycle performance of the battery, especially under high voltage conditions, the battery can still perform excellently.
The present application provides a positive electrode sheet, which includes the above-mentioned positive electrode active material, thereby helping to improve the relevant electrical performance of the battery.
The present application also provides a lithium-ion battery, which includes the above-mentioned positive electrode sheet, so the lithium-ion battery has excellent performance in terms of specific capacity and cycle performance.
The present application provides a positive electrode active material, which includes a lithium metal oxide represented by Formula 1 or Formula 2;
Lin1-y1Nay1Co1-a1-b1M1b1M2a1O2 Formula 1
Lin2-y2-b2Nay2Co1-a2M1b2M2a2O2 Formula 2
In the positive electrode active material as described above, in Formula 1, M1 is selected from one of Al, W and/or Te, B and/or P;
In the positive electrode active material as described above, the positive electrode active material is composed of a core including the lithium metal oxide and a coating layer covering at least part of a surface of the core.
In the positive electrode active material as described above, when the positive electrode active material has a cut-off voltage of 3.0-3.6V and has a SOC of zero, 0.7≤n1, n2≤1.0.
In the positive electrode active material as described above, the positive electrode active material has a median particle size of 12 μm to 20 μm.
In the positive electrode active material as described above, a first-stage discharge capacity ratio of the positive electrode active material is C1/C0≥9%, and a second-stage discharge capacity ratio is C2/C0≥25%;
In the positive electrode active material as described above, the 002 peak has a peak intensity of I1, the 131 peak has a peak intensity of I2, and I1/I2≥4.
The present application provides a positive electrode sheet, which includes the positive electrode active material according to any one of the above items.
In the positive electrode sheet as described above, the positive electrode sheet includes a positive electrode collector and a positive electrode active layer disposed on at least one surface of the positive electrode current collector, and the positive electrode active layer includes 70-99 wt % of the positive electrode active material, 0.5-15 wt % of a conductive agent, and 0.5-15 wt % of a binder by mass percentage.
In the positive electrode sheet as described above, the positive electrode active layer includes 80-98 wt % of the positive electrode active material, 1-10 wt % of a conductive agent, and 1-10 wt % of a binder by mass percentage.
This application provides a lithium-ion battery, where the lithium-ion battery includes the positive electrode sheet as described above.
In the lithium-ion battery as described above, a negative electrode sheet in the lithium-ion battery is a lithium-containing negative electrode sheet.
In the lithium-ion battery as described above, the negative electrode sheet is a lithium foil.
In the lithium-ion battery as described above, the negative electrode sheet includes a negative electrode current collector, a negative electrode active layer, and a lithium material layer, which are stacked with each other, where the negative electrode active layer is disposed on at least one surface of the negative electrode current collector, and the negative electrode active layer is close to the negative electrode current collector.
In the lithium-ion battery as described above, the lithium material layer is a lithium foil.
In the lithium-ion battery as described above, metallic lithium in the lithium material layer has a surface density of 0.09 mg/cm2 to 3.5 mg/cm2.
In the lithium-ion battery as described above, the negative electrode active layer includes 70-99 wt % of a negative electrode active material, 0.5-15 wt % of a conductive agent, and 0.5-15 wt % of a binder by mass percentage.
In the lithium-ion battery as described above, the negative electrode active layer includes 80-98 wt % of a negative electrode active material, 1-10 wt % of a conductive agent, and 1-10 wt % of a binder by mass percentage.
The positive electrode active material of the present application has a special crystal phase structure and chemical composition. After the positive electrode active material is applied to a battery, the cycle performance and gram capacity of the battery are significantly improved. Even under high voltage conditions of 4.5V and above, the battery using the positive electrode active material can still maintain excellent performance in terms of related electrical properties, and the problem of structural collapse due to poor pressure resistance of the positive electrode active material will not occur.
To make the objectives, technical solutions, and advantages of the present application clearer, the following clearly and comprehensively describes the technical solutions in embodiments of the present application in combination with the embodiments of the present application. Apparently, the described embodiments are merely a part rather than all embodiments of the present application. All other embodiments obtained by persons of ordinary skill in the art based on embodiments of the present application without creative effort shall fall within the protection scope of the present application.
In a first aspect, the present application provides a positive electrode active material, including a lithium metal oxide represented by Formula 1 or Formula 2;
Lin1-y1Nay1Co1-a1-b1M1b1M2a1O2 Formula 1
Lin2-y2-b2Nay2Co1-a2M1b2M2a2O2 Formula 2
The lithium metal oxide mentioned above in the present application is a compound having a T2 phase stacking structure, specifically an oxide at least including lithium, sodium and M1. Furthermore, it may be doped with M2. The specific selection of M2 is not limited in the present application, and M2 may be a common doping element in the art. For example, it may be at least one of the elements Mg, Ti, Mn, Al, Te, W, Ni, Nb, Zr, La, F, Ce, Sr, Y, K, B and P.
There is no more limitation on y1, y2, a1, a2, b1, b2, etc. within the above-mentioned limited range.
For example, in Formula 1, y1 is 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.010, 0.012, 0.015, 0.018, 0.020, 0.022, 0.024, 0.025, 0.026, 0.028, 0.03, 0.04 or 0.05; a1 is 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.010, 0.012, 0.015, 0.018, 0.020, 0.022, 0.024, 0.025, 0.026, 0.028, 0.030, 0.032, 0.034, 0.035, 0.04, 0.045, 0.05, 0.055, 0.06, 0.065, 0.07, 0.075, 0.08, 0.085, 0.09 or 0.095; b1 is 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.010, 0.012, 0.015, 0.018, 0.020, 0.022, 0.024, 0.025, 0.026, 0.028, 0.030, 0.032, 0.034, 0.035, 0.04, 0.045, 0.05, 0.055, 0.06, 0.065, 0.07, 0.075, 0.08, 0.085, 0.09 or 0.095; b1/1−a1−b1 is 0.005, 0.01, 0.02, 0.03, 0.04, 0.06, 0.08, 0.09, 0.095 or 0.1.
In Formula 2, y2 is 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.010, 0.012, 0.015, 0.018, 0.020, 0.022, 0.024, 0.025, 0.026, 0.028, 0.03, 0.04, or 0.05; a2 is 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.010, 0.012, 0.015, 0.018, 0.020, 0.022, 0.024, 0.025, 0.026, 0.028, 0.030, 0.032, 0.034, 0.035, 0.04, 0.045, 0.05, 0.055, 0.06, 0.065, 0.07, 0.075, 0.08, 0.085, 0.09, or 0.095; b2 is 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.010, 0.012, 0.015, 0.018, 0.02; a2/1−a2 is 0.005, 0.01, 0.02, 0.03, 0.04, 0.06, 0.08, 0.09, 0.095 or 0.1.
It should be emphasized that the above-mentioned limitations on n1 and n2 refer to parameters related to the molar amount of lithium per unit mole of the lithium metal oxide in the positive electrode active material that has not undergone any charge and discharge treatments. It can be understood that when the positive electrode active material is applied to a lithium-ion battery for any charge and discharge treatments, the molar amount of lithium in a unit mole of the lithium metal oxide is different under different charge and discharge mechanisms and charge and discharge nodes.
According to the above solutions provided in the present application, compared with other positive electrode active materials, after the positive electrode active material including the lithium metal oxide is applied to a lithium-ion battery, the specific capacity and cycle performance of the lithium-ion battery are significantly improved, and the electrical performance of the lithium-ion battery will not deteriorate even under high voltage working conditions. Based on the analysis of this phenomenon, the inventors believe that the reasons may be as below. On the one hand, the doping of M1 helps to support the structure of the lithium metal oxide, so that the structural stability of the lithium metal oxide is improved to a certain extent. Therefore, whether in normal pressure or high pressure working environment, the structurally stable lithium metal oxide is more helpful to improve the efficiency of lithium ion deintercalation and promote the improvement of the cycle performance and specific capacity of the lithium-ion battery. On the other hand, the lithium metal oxide with the above-mentioned crystal characteristics has a more complete layered crystal phase structure, which can reduce or inhibit the occurrence of internal mixing and arrangement of the crystal phase, thereby enabling lithium ions to be smoothly deintercalated, especially showing multiple small charge and discharge platforms during high-voltage charging and discharging.
Furthermore, M1 in Formula 1 is selected from one of Al, W and/or Te, B and/or P (that is, M1 is selected from any one of Al, W, Te, a blend of W and Te, B, P, or a blend of B and P); M1 in Formula 2 is K. Specifically, when M1 in Formula 1 and M1 in Formula 2 are selected from different doping elements, there are certain differences in the degree of improvement of the electrical properties related to the lithium metal oxide.
In detail, when M1 in Formula 1 contains one of Al, Te and/or W, and P, it is concluded that Al atoms, Te atoms and/or W atoms, and P atoms can replace Co atoms in the lithium metal oxide, thereby improving the structural stability of the lithium metal oxide, allowing the lithium metal oxide to successfully achieve the deintercalation of lithium ions under high pressure without structural collapse of the lithium metal oxide, and improving the specific capacity and cycle performance of the battery.
When M1 in Formula 1 contains B atoms, the embedding of B atoms can replace Co atoms in the lithium metal oxide. This has a certain degree of fluxing effect, helping to make the lithium metal oxide become single crystal morphology (i.e., primary particles), thereby increasing the compaction density of the positive electrode sheet.
When M1 in Formula 2 is selected from K atoms, it is concluded that the radius of K atoms is larger than that of Li atoms and Na atoms, and K-atom space-occupying plays a supporting role in the lithium metal oxide, which is beneficial to the deintercalation of Li ions, thereby significantly improving the cycle performance and gram capacity. In addition, by controlling the doping amount of K, the electrochemical kinetics and rate performance during battery charging and discharging can be improved, and the polarization phenomenon can be reduced. This also has a positive promoting effect on the rate performance and first efficiency.
In addition to the positive promoting effect of the lithium metal oxide on the battery-related electrical properties, the performance of the battery will be further improved, when at least part of a surface of the lithium metal oxide is covered with a coating layer. By setting the coating layer, the positive electrode active material is a core-shell structure including a core of the lithium metal oxide and the coating layer covers the core. The coating layer helps to reduce or inhibit side reactions between the lithium metal oxide and an electrolyte. Even when the battery is operating under high voltage, a stable interface can still be formed between the positive electrode active material and the electrolyte, thereby improving the battery's cycle performance by avoiding excessive precipitation of metal ions in positive electrode active ions and avoiding liquid shortage. At the same time, the inhibition or reduction of side reactions can also reduce the gas production inside the battery, thereby ensuring the safety performance of the battery.
The present application does not limit the selection of the material of the coating layer, as long as it can inhibit side reactions and ensure the normal migration of lithium ions. In order to further improve the lithium ion conductivity, the coating layer can be made of a material such as carbon-containing compounds and fast ion conductors.
As mentioned above, in the lithium metal oxide that has not undergone any charge and discharge treatments, n1 and n2 are between 0.6 and 0.8. When a positive electrode sheet including the positive electrode active material and a lithium metal negative electrode sheet is assembled into a battery that is then charged and discharged, n1 and n2 of the lithium metal oxide are between 0.7˜1.0 when the remaining power SOC of the battery is 0 (i.e., in a fully discharged state) and the discharge cut-off voltage is 3.0˜3.6V. It should be noted that the changes in n1 and n2 refer to the number of charge and discharge cycles being within 10. Specifically, after the above mentioned lithium metal oxide is subjected to charge and discharge applications, its composition will change, especially the molar amount of lithium will be significantly increased. The reason is that the lithium metal oxide having the above mentioned crystal structure has some holes, so when it is subjected to charge and discharge treatment (such as formation), its holes can receive lithium atoms from the lithium negative electrode, thereby increasing the molar amount of lithium ions compared to the situation before charge and discharge applications. This characteristic helps to further improve the battery's cycle performance and specific capacity.
The detection of the above n1 and n2 can be performed by ICP. Specifically, the discharged battery is disassembled and the positive electrode sheet is taken out, then the positive electrode sheet is soaked in dimethyl carbonate (DMC) for 1-3 hours or rinsed with DMC, dried naturally in a drying room, then calcined at 300-600° C. in a muffle furnace for 2-5 hours, and then sieved with 200 mesh to obtain a powder to be tested. Then ICP is used to detect metal elements in the powder to be tested, so as to calculate n1 and n2.
The positive electrode active material of the present application may be single crystal morphology or polycrystalline morphology, and the specific morphology is related to the selection and proportion of doping elements. Specifically, when it is polycrystalline morphology, it is a spherical or quasi-spherical particle; when it is single crystal morphology, it can be a whisker, a flake, or any other irregular shape.
Furthermore, the median particle size of the positive electrode active material in this application is 12-20 μm, such as 3 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, or 20 μm. The inventors found that when the median particle size of the positive electrode active material meets the above requirement, on the one hand, its corresponding specific surface area can meet the deintercalation of more lithium ions; on the other hand, the agglomeration phenomenon between positive electrode active material particles is effectively controlled, so that they can be stably dispersed in a slurry during the slurrying process.
The inventors found that when the lithium metal oxide meets the doping and doping ratio of the specific element M1, the multiple discharge small platforms during the charge and discharge process thereof all show relatively excellent discharge capacity.
In a specific embodiment, the first-stage discharge capacity ratio of the positive electrode active material is C1/C0≥9%, and the second-stage discharge capacity ratio is C2/C0≥25%. Among them, C0 is a discharge capacity of a half-cell including the positive electrode active material when the half-cell is subjected to a discharge treatment at a voltage of 3.0 to 4.55V; in the discharge treatment, a capacity released when the half-cell is discharged from an initial discharge voltage to 4.4V is defined as C1, and a capacity released by the half-cell when the half-cell is discharged from 3.8V to 3.7V is defined as C2. Furthermore, C1/C0≥11%, and the second stage discharge capacity ratio is C2/C0≥28%.
It should be explained that the above discharging of capacity is carried out under a special discharge mechanism. Specifically, after the half-cell including a positive electrode sheet including the positive electrode active material and a lithium metal negative electrode is charged to a SOC of 100% (without any special limitation on the charging mechanism), the half-cell is subjected to a discharge treatment at 0.1 C at 3.0-4.55V. The electric quantity released when the half-cell is discharged from 4.55V to 4.4V at 0.1 C is C1, and the electric quantity released in the voltage reduction stage when the half-cell continues to be discharged from 3.8V to 3.7V is C2. When the half-cell continues to be discharged to 3.0V (SOC is 0 at this time), the total electric quantity released from the beginning of self-discharging is C0.
It is obvious that in the discharge treatment under a high voltage environment, both the discharge capacity ratio in the first stage and the discharge capacity ratio in the second stage perform excellently. Therefore, the positive electrode active material including the lithium metal oxide of the present application has strong pressure resistance, and thus it can be subjected to a voltage-boosting treatment to increase the specific capacity of the battery.
In one embodiment, in the lithium metal oxide, the peak intensity of the 002 peak is I1, the peak intensity of the 131 peak is I2, and I1/I2≥4. At this time, the internal crystal structure of the lithium metal oxide is more perfect, which helps to improve the cycle performance of battery. Furthermore, I1/I2≥6.
The present application does not limit the preparation method of the above-mentioned lithium metal oxide. In a specific embodiment, the lithium metal oxide of the present application can be prepared by mixing a sodium metal oxide represented by Formula 1a or 2a with a lithium compound and performing ion exchange treatment, where Formula 1a is Nax1Co1-a1-b1M1b1M2a1O2, and Formula 2a is Nax2Co1-a2M1b2M2a1O2.
In Formula 1a, 0.68<x1<0.74, 0<b1<0.1, 0≤a<0.10, 0<b1/1−a1<0.05; in Formula 2a, 0.68<x2<0.74, 0<b2<0.02, 0≤a2<0.1.
The above-mentioned ion exchange treatment is a heat treatment process, specifically refers to mixing the sodium metal oxide and the lithium compound and then subjecting them to a heat treatment at 80° C. to 300° C. for no longer than 10 hours. After the ion exchange treatment, the ion-exchanged system is washed and dried to finally obtain a lithium metal oxide, where the drying temperature is 80-180° C. and the drying time is at least 10 hours. There is no limitation on the equipment for ion exchange treatment and drying equipment. For example, the equipment for ion exchange treatment can be sealing container equipment with sealing function and stirring capability, such as wet coating reaction equipment, co-precipitation reaction equipment, etc.; the drying equipment can be a blast oven, vacuum drying oven, rotary kiln, disc dryer, oven, etc.
The above-mentioned lithium compound can be a commonly used lithium source compound in the field, for example, the lithium compound is one of lithium carbonate, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, lithium hydroxide, and lithium fluoride. In the ion exchange treatment, the mass ratio of the lithium compound to the sodium metal oxide is not less than 1:1, in a possible embodiment, (1-3):1.
Furthermore, when it is necessary to prepare a positive electrode active material in which a coating layer covers outside the lithium metal oxide, a raw material of the coating layer needs to be added in addition to the raw materials including the sodium metal oxide and the lithium compound in the ion exchange process.
For the sodium metal compound shown in Formula 1a and Formula 2a, for example, it can be prepared by a method including the following process:
Specifically, the calcination treatment is performed at a temperature of 700 to 900° C., for a time of 8 to 50 hours. The calcination treatment can be performed in an oxygen or air atmosphere. The equipment for calcination treatment may be, for example, a muffle furnace, a tunnel furnace, a roller kiln, a tubular furnace or other high-temperature sintering equipment.
The mixing of the above-mentioned sources can be performed by high-speed mixing equipment, sand milling equipment, ball milling equipment, plowshare mixing equipment, tilted mixing equipment, etc. It should be noted that if sand milling equipment or ball milling equipment is used and a solvent (water, ethanol or other solvent medium) is added during the ball milling or sand milling process, the mixed system needs to be dried after the mixing process is completed. Generally, the mixing time is not more than 4 hours.
The present application does not limit the specific selection of the cobalt source, sodium source, M1 source and M2 source. For example, the cobalt source is selected from one or more of cobaltous hydroxide, cobaltosic oxide, doped cobaltosic oxide, cobaltous oxide, cobalt oxyhydroxide, cobalt nitrate, cobalt sulfate, etc.; the sodium source is selected from one or more of sodium carbonate, sodium nitrate, sodium hydroxide, sodium bicarbonate, sodium sulfate, etc.; the M1 source can be any compound containing M1, such as an oxide of M1. When M1 is W, the M1 source is, for example, tungstic acid and/or sodium tungstate, etc.; when M1 is Te, the M1 source is, for example, telluric acid and/or sodium tellurate, etc.; when M1 is Al, the M1 source is, for example, aluminum sulfate, aluminum nitrate, aluminum hydroxide, etc.; when M1 is B, the M1 source is, for example, boric acid and/or sodium borate, etc.; when M1 is P, the M1 source is, for example, phosphoric acid and/or sodium phosphate, etc.; when M1 is K, the M1 source is, for example, one or more of potassium carbonate, potassium nitrate, potassium hydroxide, potassium bicarbonate, potassium sulfate, etc.; the M2 source can be any compound containing M2, such as an oxide of M2, such as one or more of basic magnesium carbonate, magnesium hydroxide, zirconium oxide, yttrium oxide, lanthanum oxide, lanthanum fluoride, nickel oxide, niobium oxide, etc.
A second aspect of the present application provides a positive electrode sheet, which includes the positive electrode active material described in the first aspect.
Based on the characteristics of the positive electrode active material in the first aspect, the positive electrode sheet of the present application helps to improve the cycle performance and specific capacity of lithium-ion batteries.
In a specific embodiment, the positive electrode sheet of the present application includes a positive electrode current collector and a positive electrode active layer disposed on at least one surface of the positive electrode current collector, and the positive electrode active layer includes the above-mentioned positive electrode active material.
It can be understood that in addition to the positive electrode active material, the positive electrode active layer includes a conductive agent and a binder. For example, the positive electrode active layer includes 70-99 wt % of the positive electrode active material, 0.5-15 wt % of a conductive agent, and 0.5-15 wt % of a binder by mass percentage. Furthermore, it includes 80-98 wt % of the positive electrode active material, 1-10 wt % of a conductive agent, and 1-10 wt % of a binder.
There is no particular preference for the conductive agent and the binder, and they may be conventionally selected in the art. For example, the conductive agent is selected from at least one of conductive carbon black, acetylene black, Ketjen black, conductive graphite, conductive carbon fiber, carbon nanotubes, single-walled carbon nanotubes, multi-arm carbon nanotubes, and carbon fibers, and the binder is selected from at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyacrylate lithium (PAALi).
Furthermore, in order to improve safety performance, a safety layer may be provided between the positive electrode active layer and the current collector. The material of the safety layer is generally a non-conductive safety material, such as iron-containing compounds (such as lithium iron phosphate, lithium phosphate, etc.), aluminum-containing compounds (such as ceramic aluminum oxide), etc. Of course, the safety layer also includes a binder, and the ratio of the binder to the safety material can be further determined according to specific needs.
The third aspect of the present application also provides a lithium-ion battery, which includes the above-mentioned positive electrode sheet and thus has outstanding performance in terms of cycle performance and specific capacity.
The present application does not limit the specific structure of the lithium-ion battery, for example, it can be a square shell battery, a cylindrical battery, etc.
According to the present application, the lithium-ion battery further includes a negative electrode sheet, a separator and an electrolyte.
For example, the electrolyte is a conventional electrolyte known in the art, including a lithium salt and a solvent, and the solvent contains ethylene carbonate (abbreviated as EC), diethyl carbonate (abbreviated as DEC), propylene carbonate (abbreviated as PC), and fluoroethylene carbonate (abbreviated as FEC). Furthermore, it also includes an additive represented by Formula T, whose mass percentage in the electrolyte is 0.1-10%,
For example, the negative electrode sheet may be a negative electrode sheet containing lithium metal, for example, it may be a lithium foil or a negative electrode sheet as shown in
In a specific embodiment, the negative electrode active layer includes 70-99 wt % of a positive electrode active material, 0.5-15 wt % of a conductive agent, and 0.5-15 wt % of a binder by mass percentage. Furthermore, it includes 80-98 wt % of a negative electrode active material, 1-10 wt % of a conductive agent, and 1-10 wt % of a binder. The negative electrode active material is selected from one or more of artificial graphite, natural graphite, hard carbon, mesophase carbon microbeads, lithium titanate, silicon carbon, and silicon (II) oxide.
For example, the separator is a material with polypropylene as the base material, or a gummed separator with ceramic coated on one side or both sides thereof.
The lithium-ion battery of the present application is applicable to a high-voltage system, specifically, a lithium-ion button battery including the above mentioned positive electrode sheet under the condition of ≥4.55V (relative to lithium) has a gram capacity of ≥225 mAh/g and excellent cycling performance at ≥4.50V (corresponding to the above mentioned negative electrode sheet) at the same time.
Therefore, the lithium-ion battery of the present application has good cycle stability and high gram capacity at higher voltages such as 4.50V, which can meet the demand for lightweight and thin use of high-end digital products.
Hereinafter, the positive electrode active material of the present application is introduced through specific Examples.
A preparation method of a positive electrode material provided in this example includes the following steps:
ICP is used to detect and analyze 1A #, the specific results of which are shown in Table 1A.
The preparation methods of Examples 2A-9A are basically the same as that of Example 1A, and the difference only lies in the selection of different M1 (W source or Te source) and M2 sources, as well as the mass ratios between the individual metal sources, in step (1). The specific selection is shown in Table 1A, and samples 2A #-9A #are finally obtained. And their ICP detection and analysis results are shown in Table 1A.
The preparation method of Example 10A is basically the same as that of Example 1A, and the difference only lies in that the step (1) is: weighing 36.56 g of a sodium carbonate powder, 4.593 g of a tellurium acid powder, and 79.30 g of a compound of aluminum-doped cobaltosic oxide (Co0.95Al0.03)3O4, putting them into a high-speed mixing device, setting a mixing program, mixing them at 300 rpm for 3 minutes, at 500 rpm for 5 minutes, at 1000 rpm for 10 minutes, then taking out the mixture, and confirming that there is no small white spot of white sodium carbonate in the mixture, so as to confirm that the mixture is uniform.
The final sodium metal oxide obtained in the step 2) is Na0.69Co0.95Te0.02Al0.03O2 and the sample 10A #is Li0.71Na0.02Co0.95Te0.02Al0.03O2.
The preparation method of Example 11A is basically the same as that of Example 10A, and the difference only lies in that the step (3) is: preparing a reaction container, weighing 10.49 g of lithium hydroxide monohydrate and 17.24 g of lithium nitrate particles, adding the two lithium compounds separately into the reaction container, weighing 10 g of Na0.69Co0.95Te0.02Al0.03O2 synthesized in step (2), adding it into the reaction container, mixing them preliminarily, then performing ion exchange at 280° C. for 1 hour to obtain a crude product; after the treatment in step (4), a sample 11A #Li0.71Na0.02Co0.95Te0.02Al0.03O2 is obtained.
The preparation method of Example 12A is basically the same as that of Example 10A, and the difference only lies in that the step (3) is: preparing a reaction container, weighing 10.49 g of lithium hydroxide monohydrate and 9.24 g of lithium carbonate particles, adding the two lithium compounds separately into the reaction container, weighing 10 g of Na0.69Co0.95Te0.02Al0.03O2 synthesized in step (2), adding it into the reaction container, mixing them preliminarily, then performing ion exchange at 280° C. for 1 hour to obtain a crude product; after the treatment in step (4), a sample 12A #Li0.71Na0.0.02Co0.95Te0.02Al0.03O2 is obtained.
The preparation method of Example 13A is basically the same as that of Example 10A, and the difference only lies in that the step (3) is: preparing a reaction container, weighing 10.49 g of lithium hydroxide monohydrate and 10.59 g of lithium chloride particles, adding the two lithium compounds separately into the reaction container, weighing 10 g of Na0.69Co0.95Te0.02Al0.03O2 synthesized in step (2), adding it into the reaction container, mixing them preliminarily, then performing ion exchange at 280° C. for 1 hour to obtain a crude product; after the treatment in step (4), a sample 13A #Li0.71Na0.0.02Co0.95Te0.02Al0.03O2 is obtained.
A preparation method of a positive electrode material provided in this example includes the following steps:
ICP is used to detect and analyze 1B #, the specific results of which are shown in Table 1B.
The preparation methods of Examples 2B-9B are basically the same as that of Example 1B, and the difference only lies in the selection of different M2 sources as well as the mass ratios between the individual metal sources, in step (1). The specific selection is shown in Table 1B, and samples 2B #-9B #are finally obtained, and their ICP detection and analysis results are shown in Table 1B.
The preparation method of Example 10B is basically the same as that of Example 1B, and the difference only lies in that the step (1) is: weighing 36.56 g of a sodium carbonate powder, and 79.30 g of a compound of aluminum-doped cobaltosic oxide (Co0.95Al0.03)3O4, putting them into a high-speed mixing device, setting a mixing program, mixing them at 300 rpm for 3 minutes, at 500 rpm for 5 minutes, at 1000 rpm for 10 minutes, and then taking out the mixture, and confirming that there is no small white spot of white sodium carbonate in the mixture, so as to confirm that the mixture is uniform.
The final sodium metal oxide obtained in step (2) is Na0.69Co0.97Al0.03O2 and the sample 10B #is Li0.71Na0.02Co0.97Al0.03O2.
The preparation method of Example 11B is basically the same as that of Example 10B, and the difference only lies in that the ion exchange time in step (3) is 1 hour. The obtained sample 11B #is Li0.71Na0.02Co0.97Al0.03O2.
The preparation method of Example 12B is basically the same as that of Example 10B, and the difference only lies in that 9.24 g of lithium carbonate particles are used to replace 17.24 g of lithium nitrate particles in step (3). The obtained sample 12B #is Li0.71Na0.02Co0.97Al0.03O2.
The preparation method of Example 13B is basically the same as that of Example 10B, and the difference only lies in that 10.59 g of lithium chloride particles are used to replace 17.24 g of lithium nitrate particles in step (3). The obtained sample 13B #is Li0.71Na0.02Co0.97Al0.03O2.
A preparation method of a positive electrode material provided in this example includes the following steps:
ICP is used to detect and analyze 1C #, the specific results of which are shown in Table 1C.
The preparation methods of Examples 2C-9C are basically the same as that of Example 1C, and the difference only lies in the selection of different M1 (B source or P source) and M2 sources, as well as the mass ratios between the individual metal sources, in step (1). The specific selection is shown in Table 1C, and the samples 2C #-9C #are finally obtained, and their ICP detection and analysis results are shown in Table 1C.
The preparation method of Example 10C is basically the same as that of Example 1C, and the difference only lies in that the step (1) is: weighing 36.56 g of a sodium carbonate powder, 1.236 g of a boric acid powder, and 79.30 g of a compound of aluminum-doped cobaltosic oxide (Co0.95Al0.03)3O4, putting them into a high-speed mixing device, setting a mixing program, mixing them at 300 rpm for 3 minutes, at 500 rpm for 5 minutes, at 1000 rpm for 10 minutes, and then taking out the mixture, and confirming that there is no small white spot of white sodium carbonate in the mixture, so as to confirm that the mixture is uniform.
The final sodium metal oxide obtained in step 2) is Na0.69Co0.95B0.02Al0.03O2 and the sample 10C #is Li0.71Na0.02Co0.95B0.02Al0.03O2.
The preparation method of Example 11C is basically the same as that of Example 10C, and the difference only lies in that the ion exchange time in step (3) is 1 hour. The obtained sample 11C #is Li0.71Na0.02Co0.95B0.02Al0.03O2.
The preparation method of Example 12C is basically the same as that of Example 10C, and the difference only lies in that 9.24 g of lithium carbonate particles are used to replace 17.24 g of lithium nitrate particles in step (3). The obtained sample 12C #is Li0.71Na0.02Co0.95B0.02Al0.03O2.
The preparation method of Example 13C is basically the same as that of Example 10C, and the difference only lies in that 10.59 g of lithium chloride particles are used to replace 17.24 g of lithium nitrate particles in step (3). The obtained sample 13C #is Li0.71Na0.02Co0.95B0.02Al0.03O2.
A preparation method of a positive electrode material provided in this example includes the following steps:
ICP is used to detect and analyze 1D #, the specific results of which are shown in Table 1D.
The preparation methods of Examples 2D-9D are basically the same as that of Example 1D, and the difference only lies in the selection of different M2 sources, as well as the mass ratios between the individual metal sources, in step (1). The specific selection is shown in Table 1D, and the samples 2D #-9D #are finally obtained, and their ICP detection and analysis results are shown in Table 1D.
The preparation method of Example 10D is basically the same as that of Example 1D, and the difference only lies in that the ion exchange time in step (3) is 1 hour. The obtained sample 10D #is Li0.71Na0.02K0.003Co0.97Mg0.03O2.
The preparation method of Example 11D is basically the same as that of Example 1D, and the difference only lies in that the ion exchange temperature in step (3) is 260° C. The obtained sample 10D #is Li0.71Na0.02K0.003Co0.97Mg0.03O2.
The preparation method of Example 12D is basically the same as that of Example 1D, and the difference only lies in that 9.24 g of lithium carbonate particles are used to replace 17.24 g of lithium nitrate particles in step (3). The obtained sample 12D #is Li0.71Na0.02K0.003Co0.97Mg0.03O2.
The preparation method of Example 13D is basically the same as that of Example 1D, and the difference only lies in that 10.59 g of lithium chloride particles are used to replace 17.24 g of lithium nitrate particles in step (3). The obtained sample 13D #is Li0.71Na0.02K0.003Co0.97Mg0.03O2.
The unfilled parts in Tables 1A-1D represent that the raw materials of these Examples do not include compounds.
The chemical composition of a positive electrode material provided by this Comparative Example is Li1.0026CoO2;
The preparation method thereof includes the following steps:
The positive electrode material provided by this Comparative Example is a conventional high-voltage doped and coated lithium cobaltate positive electrode material, with a chemical composition of Li1.0027Co0.97Al0.03O2;
The preparation method of the positive electrode material includes the following steps:
The preparation method of Comparative Example 3 is basically the same as that of Example 1A, and the difference only lies in that step (1) is: weighing 36.56 g of a sodium carbonate powder and 291.05 g of a cobalt nitrate hexahydrate powder, without adding any additives, putting them into a high-speed mixing device, setting a mixing program, mixing them at 300 rpm for 3 minutes, at 500 rpm for 5 minutes, and at 1000 rpm for 10 minutes, and then taking out the mixture, and confirming that there is no small white spot of white lithium carbonate in the mixture, so as to confirm that the mixture is uniform.
After the treatments in steps (2) to (4), a product having a T2 structure for Comparative Example 3 is obtained with a chemical formula of Li0.71Na0.02CoO2.
The positive electrode material provided by this Comparative Example is conventional high-voltage doped and coated lithium cobaltate positive electrode material, with a chemical composition of Li1.0027Co0.947K0.003Mg0.03La0.02O2.
The preparation method thereof includes the following steps:
XRD diffraction is performed on the products of all the Examples and Comparative Examples, and the results are shown in Tables 2A to 2D.
After the products in all the Examples and Comparative Examples are made into positive electrode sheets, they are assembled with negative electrode sheets, electrolytes and separators according to the following method to obtain lithium-ion batteries. The method includes following steps:
Where the electrolyte is a conventional electrolyte known in the art, which is formed by mixing ethylene carbonate (abbreviated as EC), diethyl carbonate (abbreviated as DEC), and propylene carbonate (abbreviated as PC) in a mass ratio of 2:5:3, and then adding fluoroethylene carbonate (abbreviated as FEC) at 5% of the total mass of the electrolyte, lithium hexafluorophosphate (abbreviated as LiPF6) at 13% of the total mass of the electrolyte, and an additive represented by formula T with an additive content of 2% of the total mass of the electrolyte.
The capacity retention rate of each lithium-ion battery obtained is tested. The specific test method is charging to 4.50V at a constant current with a charging ratio of 1 C at 25° C., then charging to 4.50V at a constant voltage with a charging ratio of 0.05 C, and then discharging to 3.0V with a discharging ratio of 1 C, and repeating this charging and discharging cycle for 500 times, and measuring the discharging capacity at the first cycle and at the 500th cycle, and then calculating the capacity retention rate after cycles of 500 times according to the following formula. The results are shown in Tables 2A-2D.
Capacity retention rate Q=(discharge capacity at the 500th cycle)/(discharge capacity at the first cycle)*100%
After the products in all the Examples and Comparative Examples are made into positive electrode sheets, they are assembled with negative electrode sheets, electrolytes and separators according to the following method to obtain button batteries. The method includes following steps:
Each button battery is left standing for 4 hours under conventional conditions, then the first charge and discharge capacity test is carried out. The test conditions are: charging at 0.1 C to 4.55V, constant-voltage charging to 0.025 C for cut-off, and leaving it standing for 3 minutes, and then discharging at 0.1 C to 3.0V. During the discharging process, a discharging capacity C1 at 4.4-4.55V, a discharge capacity C2 at 3.7-3.8V, a first discharging full capacity CO, and a first charging capacity are recorded respectively, and the first efficiency, the first-stage discharging capacity ratio C1/C0, and the second-stage discharging capacity ratio C2/C0 are calculated. The results are shown in Tables 2A˜2D.
The products in all the Examples and Comparative Examples are assembled into lithium-ion batteries according to the method in Test Example 2. Then each lithium-ion battery is subjected to a chemical formation process, and then discharged at a current of 1/10 of a rated capacity to 3.0V, and then is subjected to voltage test. It is found that its voltage is 3.0˜3.6V. Then, the lithium-ion battery is disassembled, and the positive electrode sheet is taken out and soaked in dimethyl carbonate (DMC) for 3 hours or rinsed with DMC, dried naturally in a drying room, and then placed in a muffle furnace for roasting at 300° C. for 3 hours, then sieved through a 200-mesh sieve, so as to obtain a sample powder. ICP is used to test the content of each element in the sample powder, and n is calculated based on the detection values of elements Li, Na and, etc. The results are shown in Tables 2A˜2D.
In Tables 2A-2D, “/” indicates that there is no such parameter.
According to Tables 2A˜2D, the followings can be known.
1. According to Examples 1 (ABCD) to 9 (ABCD), although the selection and ratio of different M1 and M2 sources have a certain influence on the composition and crystal structure of the synthesized lithium metal oxide, the gram capacity and cycle performance of the lithium-ion batteries in the Examples under high voltage (4.5V, 4.55V and above voltage system) are outstanding compared with the Comparative Examples.
it should be emphasized that although the product of Comparative Example 3 has a crystal structure substantially the same as that of the Examples, its performance in terms of gram capacity and cycle performance is still somewhat different from that of the Examples, since it has no doping with specific elements.
2. According to the comparison between Example 1 (ABCD) and Examples 10 to 13 (ABCD), different preparation parameters such as reaction temperature, reaction time, and raw material selection have certain effects on the composition and crystal structure of the lithium metal oxides, and ultimately affect the relevant performance of lithium-ion batteries;
3. Although Comparative Example 3 has a 002 peak and 131 peak, the ratio of intensity of the 002 peak to 131 peak is obviously lower due to the absence of M1 doping element, so its performance in cycle performance is not ideal.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202211072411.2 | Sep 2022 | CN | national |
This application is a continuation of International Application No. PCT/CN2023/111591, filed on Aug. 7, 2023, which claims priority to Chinese Patent Application No. 202211072411.2, filed on Sep. 2, 2022. The disclosures of the aforementioned applications are hereby incorporated by reference in their entireties.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2023/111591 | Aug 2023 | WO |
| Child | 18948294 | US |
