High-compaction positive electrode material precursor and preparation method therefor, positive electrode material, battery, and powered device

Abstract

The present disclosure relates to the field of batteries and provides a high-compaction positive electrode material precursor and a preparation method therefor, a positive electrode material, a battery, and a powered device. The high-compaction positive electrode material precursor comprises first-type particles having a particle size less than 5 μm and second-type particles having a particle size greater than or equal to 5 μm, wherein the ratio of the proportion of the number of the first-type particles to the proportion of the number of the second-type particles is (10-40):1. The preparation method for the high-compaction positive electrode material precursor comprises: mixing two or more types of precursor particles to obtain the high-compaction positive electrode material precursor. According to the high-compaction positive electrode material precursor provided by the present disclosure, within appropriate number proportion ranges of particles having different particle sizes in the precursor, the effect of filling gaps between large particles with more small particles is ideal, and when the particle size range of the small particles is appropriate, an overall high compaction density is exhibited.

Description

High-density cathode material precursor and preparation method thereof, cathode material, battery and electrical equipment

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This disclosure claims priority to application number 2023118131340 filed with the Patent Office of China on December 26, 2023, entitled “High-pressure compacted positive electrode material precursor and its preparation method, positive electrode material, battery and electrical-related equipment,” the entire contents of which are incorporated by reference into this disclosure. Technical Field

[0003] The present disclosure relates to the field of batteries, and in particular to a high-density cathode material precursor and a preparation method thereof, a cathode material, a battery, and electrical equipment. Background Art

[0004] With the development of lithium-ion batteries, many types of positive electrode materials are now used in the market, such as lithium iron phosphate, lithium cobalt oxide, and lithium nickel cobalt manganese oxide.

[0005] Lithium-ion power batteries have been widely used in various devices due to their advantages such as high energy, high battery voltage, wide operating temperature range and long storage life.

[0006] At present, the main application scenario of ternary positive electrode materials is the field of power batteries, and the field of power batteries pays more attention to the high compaction performance indicators of the materials.

[0007] Therefore, developing a high-density cathode material and its precursor has become one of the research focuses.

[0008] In view of this, the present disclosure is proposed. Summary of the Invention

[0009] The purpose of the present disclosure is to provide a high-density cathode material precursor and a preparation method thereof, a lithium-ion battery and a lithium-ion battery device to solve the above problems.

[0010] To achieve the above objectives, the present disclosure adopts the following technical solutions:

[0011] A high-density cathode material precursor comprising first-type particles having a particle size of less than 5 μm and second-type particles having a particle size of greater than or equal to 5 μm;

[0012] The ratio of the number of the first type of particles to the number of the second type of particles is (10-40):1.

[0013] Optionally, the high-density cathode material precursor satisfies at least one of the following conditions:

[0014] (1) The proportion of the first type of particles is 90%-99.9%, and optionally 92-98%;

[0015] (2) The amount of the second type of particles accounts for 1%-10%, and can be 5%-10%;

[0016] (3) The particle size of the second type of particles is 5-30 μm;

[0017] (4) The ratio of the number of the first type of particles to the number of the second type of particles is (11.5-22.5):1; optionally (13.5-18.0):1.

[0018] Optionally, the particle size distribution test graph of the high-density cathode material precursor (the relationship between the particle size and the corresponding number density tested in the particle size distribution test graph of the present disclosure) has a first peak and a second peak, and the first peak and the second peak satisfy at least one of the following conditions:

[0019] (5) The particle size corresponding to the highest number percentage of the first peak is 1-5 μm, and optionally 1-3 μm;

[0020] (6) The particle size corresponding to the highest number percentage of the second peak is 6-20 μm, and can be 7-15 μm.

[0021] Optionally, the first peak and the second peak satisfy at least one of the following conditions:

[0022] (7) The ratio of the number of particles corresponding to the first peak to the number of particles corresponding to the second peak is (10-50):1, optionally (10-30):1;

[0023] (8) The ratio of the highest number proportion of the first peak to the highest number proportion of the second peak is (10-40):1, optionally (10-20):1.

[0024] Optionally, the high-density cathode material precursor meets one or more of the following conditions:

[0025] A. The compaction density of the high-compacted positive electrode material precursor is not less than 3.3 g / cm 3 , optional not less than 3.6g / cm 3 ;

[0026] B. The D50 of the high-density cathode material precursor is 8-20 μm;

[0027] C. The specific surface area BET of the high-density cathode material precursor is 5-15m 2 / g;

[0028] D. The tap density TD of the high-density positive electrode material precursor is not less than 2.3 g / cm 3 ;

[0029] E. The high-density cathode material precursor includes a compound containing nickel, which may be nickel-cobalt-manganese hydroxide.

[0030] The present disclosure also provides a method for preparing the high-density cathode material precursor, comprising:

[0031] Two or more precursor particles are mixed to obtain the high-density cathode material precursor.

[0032] Optionally, the mixing includes: mixing type A precursor particles and type B precursor particles to obtain the high-density cathode material precursor;

[0033] The type A precursor particles and the type B precursor particles meet one or more of the following conditions:

[0034] (1) The mass ratio of the type A precursor particles to the type B precursor particles is (1.5-6):1;

[0035] (2) The D50 of the Class A precursor particles is 12-25 μm, optionally 14-20 μm;

[0036] (3) The Span value ((D90-D10) / D50) of the Class A precursor particles is 0.3-1.5, optionally 0.3-0.5 or 1.0-1.5;

[0037] (4) The D50 of the type B precursor particles is 1.0-8.0 μm, optionally 3.0-6.0 μm;

[0038] (5) The Span value ((D90-D10) / D50) of the type B precursor particles is 0.4-1.5, and can be optionally 0.5-0.8 or 1.0-1.5.

[0039] The present disclosure also provides a high-density cathode material, the raw materials of which include the high-density cathode material precursor.

[0040] The present disclosure also provides a battery comprising the high-density cathode material.

[0041] The present disclosure also provides an electrical device, comprising the battery.

[0042] Compared with the prior art, the advantages of the present invention include:

[0043] The high-compacted positive electrode material precursor provided by the present invention is configured with particles having a particle size less than 5 μm and particles having a particle size greater than or equal to 5 μm and controlling the ratio of their number proportions, so that the precursors of different particle sizes are within an appropriate number proportion range, and a larger number of small particles has an ideal filling effect on the gaps between large particles, thereby overall feedback showing that the positive electrode material precursor has a higher compaction density.

[0044] The present disclosure provides a method for preparing a high-density cathode material precursor, which obtains a high-density cathode material precursor by mixing a plurality of precursor particles, and the process is simple.

[0045] The high-density cathode material provided by the present disclosure inherits the advantages of the high-density cathode material of the precursor.

[0046] The battery and electrical equipment provided by the present disclosure have excellent electrical performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present disclosure and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without creative work.

[0048] FIG1 is a number density distribution diagram of Examples 1-5;

[0049] FIG2 is a graph showing the percentage of particles of different sizes in Examples 1-5;

[0050] FIG3 is a number density distribution diagram of Example 2-1;

[0051] Figure 4 is a graph showing the percentage of particles of different sizes in Example 2-1;

[0052] Figure 5 is a graph showing the percentage of particles of different sizes in Example 3-1;

[0053] Figure 6 is a graph showing the percentage of particles of different sizes in Example 4-1;

[0054] Figure 7 is a graph showing the percentage of different particle sizes in Comparative Example 1-1;

[0055] FIG8 is a graph showing the percentage of different particle sizes in comparative example 2-2. DETAILED DESCRIPTION

[0056] The embodiments of the present disclosure will be described in detail below with reference to the examples. However, those skilled in the art will appreciate that the following examples are intended only to illustrate the present disclosure and should not be construed as limiting the scope of the present disclosure. Where specific conditions are not specified in the examples, the experiments were performed under conventional conditions or the conditions recommended by the manufacturer. Where the manufacturer of the reagents or instruments is not specified, all are commercially available conventional products.

[0057] The endpoints of the ranges and any values ​​disclosed in this disclosure are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be considered to be specifically disclosed herein.

[0058] The present disclosure provides a high-density cathode material precursor, comprising a first type of particles having a particle size of less than 5 μm and a second type of particles having a particle size of greater than or equal to 5 μm;

[0059] The ratio of the number of the first type of particles to the number of the second type of particles is (10-40):1.

[0060] Optionally, the ratio of the number of the first type of particles to the number of the second type of particles can be 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1 or any value between (10-40):1.

[0061] In an optional embodiment, the high-density cathode material precursor satisfies at least one of the following conditions:

[0062] (1) The proportion of the first type of particles is 90%-99.9%, and optionally 92-98%;

[0063] Optionally, the proportion of the first type of particles may be 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.9% or any value between 90% and 99.9%;

[0064] (2) The amount of the second type of particles accounts for 1%-10%, and can be 5%-10%;

[0065] Optionally, the proportion of the second type of particles may be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or any value between 1% and 10%;

[0066] (3) The particle size of the second type of particles is 5-30 μm;

[0067] Optionally, the particle size of the second type of particles may be 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, or any value between 5 and 30 μm;

[0068] (4) The ratio of the number of the first type of particles to the number of the second type of particles is (11.5-22.5):1, optionally (13.5-18.0):1.

[0069] In an optional embodiment, the particle size distribution test graph of the high-density cathode material precursor has a first peak and a second peak, and the first peak and the second peak satisfy at least one of the following conditions:

[0070] (5) The particle size corresponding to the highest number percentage of the first peak is 1-5 μm, and optionally 1-3 μm;

[0071] (6) The particle size corresponding to the highest number percentage of the second peak is 6-20 μm, and can be 7-15 μm.

[0072] Optionally, the particle size corresponding to the highest number proportion of the first peak is in any range between 1-2 μm, 1-3 μm, 1-4 μm, 2-5 μm or 1-5 μm, and the particle size corresponding to the highest number proportion of the second peak is in any range between 6-10 μm, 7-15 μm, 8-20 μm or 6-20 μm.

[0073] In an optional embodiment, the first peak and the second peak satisfy at least one of the following conditions:

[0074] (7) The ratio of the number of particles corresponding to the first peak to the number of particles corresponding to the second peak is (10-50):1, optionally (10-30):1;

[0075] (8) The ratio of the highest number proportion of the first peak to the highest number proportion of the second peak is (10-40):1, optionally (10-20):1.

[0076] Optional bimodal distribution, with the first peak and the second peak accounting for a large proportion, indicates that the number of small particles is dominant. A larger number of small particles has an ideal filling effect on the gaps between large particles, resulting in high compaction density. In addition, the large proportion of small particles also provides the characteristics of short ion migration channels and fast migration rates of small particles after mixing, making it easy to exhibit excellent rate performance.

[0077] It should be noted that the dividing line between the first peak and the second peak is a straight line perpendicular to the horizontal axis and the lowest point (ie, the inflection point) between the highest points of the two peaks.

[0078] Optionally, the ratio of the number of secondary particles corresponding to the first peak to the number of secondary particles corresponding to the second peak can be any value between 10:1, 20:1, 30:1, 40:1, 50:1 or (10-50):1, and the ratio of the highest number of the first peak to the highest number of the second peak can be any value between 10:1, 20:1, 30:1, 40:1 or (10-40):1.

[0079] In an optional embodiment, the high-density cathode material precursor satisfies one or more of the following conditions:

[0080] A. The compaction density of the high-compacted positive electrode material precursor is not less than 3.3 g / cm 3 , optional not less than 3.6g / cm 3 ;

[0081] For example, the compaction density of the high-compacted cathode material precursor can be 3.3 g / cm 3 、3.4g / cm 3 、3.5g / cm 3 、3.6g / cm 3 、3.7g / cm 3 、3.8g / cm 3 、3.9g / cm 3 , 4.0g / cm 3 or not less than 3.3g / cm 3 The value of .

[0082] The high packing density is reflected in the battery performance as an extremely high discharge specific capacity.

[0083] B. The D50 of the high-density cathode material precursor is 8-20 μm;

[0084] Optionally, the D50 of the high-density cathode material precursor may be 8 μm, 10 μm, 15 μm, 20 μm, or any value between 8 and 20 μm;

[0085] C. The specific surface area BET of the high-density cathode material precursor is 5-15m 2 / g;

[0086] Optionally, the BET of the high-density cathode material precursor may be 5m 2 / g、10m 2 / g、15m 2 / g or 5-15m 2 Any value between / g;

[0087] D. The tap density TD of the high-density positive electrode material precursor is not less than 2.3 g / cm3 ;

[0088] For example, the TD of a high-density cathode material precursor can be 2.3 g / cm 3 , 2.4g / cm 3 , 2.5g / cm 3 , 2.6g / cm 3 , 2.7g / cm 3 , 2.8g / cm 3 , 2.9g / cm 3 , 3.0g / cm 3 or not less than 2.3g / cm 3 The value of

[0089] E. The high-density cathode material precursor includes a compound containing nickel, which may be nickel-cobalt-manganese hydroxide.

[0090] The present disclosure also provides a method for preparing the high-density cathode material precursor, comprising:

[0091] Two or more precursor particles are mixed to obtain the high-density cathode material precursor.

[0092] It should be noted that the particle size of the precursor particles referred to here does not need to strictly correspond to the particle size range of the first type of particles and the second type of particles. It only requires that the high-density positive electrode material precursor obtained by mixing can meet the particle size range of the first type of particles and the second type of particles when divided according to the particle size.

[0093] In an optional embodiment, the mixing includes: mixing type A precursor particles and type B precursor particles to obtain the high-density cathode material precursor;

[0094] The type A precursor particles and the type B precursor particles meet one or more of the following conditions:

[0095] (1) The mass ratio of the type A precursor particles to the type B precursor particles is (1.5-6):1;

[0096] (2) The D50 of the Class A precursor particles is 12-25 μm, optionally 14-20 μm;

[0097] (3) The Span of the Class A precursor particles is 0.3-1.5, optionally 0.3-0.5 or 1.0-1.5;

[0098] (4) The D50 of the type B precursor particles is 1.0-8.0 μm, optionally 3.0-6.0 μm;

[0099] (5) The Span of the type B precursor particles is 0.4-1.5, and can be optionally 0.5-0.8 or 1.0-1.5.

[0100] Optionally, the mass ratio of the class A precursor particles to the class B precursor particles can be 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1 or any value between (1.5-6):1; the D50 of the class A precursor particles can be 12 μm, 15 μm, 20 μm, 25 μm or any value between 12-25 μm; the Span of the class A precursor particles can be 0.3, 0.5, 1.0, 1 .5 or any value between 0.3-1.5; the D50 of the type B precursor particles can be 1.0μm, 2.0μm, 3.0μm, 4.0μm, 5.0μm, 6.0μm, 7.0μm, 8.0μm or any value between 1.0-8.0μm; the Span of the type B precursor particles can be 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5 or any value between 0.4-1.5.

[0101] The present disclosure also provides a high-density cathode material, the raw materials of which include the high-density cathode material precursor.

[0102] The present disclosure also provides a battery comprising the high-density cathode material.

[0103] The present disclosure also provides an electrical device, comprising the battery.

[0104] The embodiments of the present disclosure will be described in detail below with reference to specific examples. However, those skilled in the art will appreciate that the following examples are intended only to illustrate the present disclosure and should not be construed as limiting the scope of the present disclosure. Where specific conditions are not specified in the examples, conventional conditions or conditions recommended by the manufacturer were used. Reagents or instruments used where the manufacturer is not specified are conventional products that can be purchased commercially.

[0105] Example 1-1

[0106] (1) Preparation of Class A particles: nickel salt, cobalt salt and manganese salt are prepared into a metal salt solution according to the molar ratio of Ni:Co:Mn=88:9:3, wherein the sum of the mass concentration of metal ions is 120g / L. Pure water, sodium hydroxide solution (mass percentage concentration of 20.0%) and ammonia solution (mass percentage concentration of 16.4%) are added into the reactor to prepare a bottom solution with a pH value of 12.2 and an ammonia mass concentration of 9.4g / L; nitrogen is introduced as a protective gas, the reaction temperature is 70-80℃, the stirring speed of the reaction process is adjusted to 410r / min, the metal salt solution is introduced at a set flow rate of 15L / min, the flow rate of sodium hydroxide solution is adjusted to 2.46L / h and the flow rate of ammonia is adjusted to 0.81L / h, so that the pH in the reactor is maintained between 12.1-12.3, the slurry particle size D50 is measured to be 14μm, then the reaction is stopped, and the nickel-cobalt-manganese precursor is obtained after post-treatment: Ni 0.88 Co 0.09 Mn 0.03 (OH)2.

[0107] (2) Preparation of Class B Particles: A metal salt solution was prepared by mixing nickel salt, cobalt salt, and manganese salt in a molar ratio of Ni:Co:Mn = 79:12:9, wherein the total mass concentration of the metal ions was 120 g / L. Pure water, sodium hydroxide solution (20.0% by mass), and ammonia solution (16.4% by mass) were added to a reactor to prepare a base solution having a pH of 11.92 and an ammonia concentration of 6.0 g / L. Nitrogen was introduced as a protective gas, and the reaction temperature was 50-55°C. The stirring speed of the reaction process was adjusted to 331 r / min, and the metal salt solution was introduced at a set flow rate of 10 L / min, the flow rate of the sodium hydroxide solution was adjusted to 2.16 L / h, and the flow rate of the ammonia water was adjusted to 0.78 L / h, so that the pH in the reactor was maintained between 10.4 and 10.6. The slurry particle size D50 was measured to be 3.8 μm, and the reaction was stopped. After post-treatment, the nickel-cobalt-manganese precursor was obtained: Ni 0.79 Co 0.12 Mn 0.09 (OH)2.

[0108] (3) The type A particles and the type B particles are uniformly mixed in a mass ratio of 6:4 to obtain the high-density positive electrode material precursor.

[0109] Example 1-2 to Example 1-6

[0110] Examples 1-2 to 1-5: The difference from Example 1-1 is that the mass ratio of the mixture of type A particles and type B particles is different. The specific ratio is shown in Table 1.

[0111] Example 1-6: The difference from Example 1-1 is: 1) Type A particles: the reaction is stopped when the particle size D50 is 17.4 μm; 2) the mass ratio of the mixture of Type A particles and Type B particles is different, see Table 1 for the specific ratio.

[0112] Example 2-1

[0113] (1) Preparation of Class A particles: nickel salt, cobalt salt and manganese salt are prepared into a metal salt solution according to the molar ratio of Ni:Co:Mn=88:9:3, wherein the sum of the metal ion mass concentrations is 120 g / L.

[0114] Step 1: Add pure water, sodium hydroxide solution (mass percentage concentration of 20.0%) and ammonia solution (mass percentage concentration of 16.4%) into the reactor to prepare a first bottom liquid with a pH value of 9-10 and an ammonia mass concentration of 8.0 g / L; the stirring speed is 370 r / min; the first bottom liquid is protected by inert gas, and the metal salt mixed solution, ammonia water and NaOH solution are added to the first bottom liquid reactor. The reaction temperature is 40-45°C, and the feeding and discharging are continuous. During the reaction process, the pH is controlled to be within the range of 9.0-9.3 and the ammonia concentration fluctuates within the range of 8-9 g / L by fine-tuning the flow rate of ammonia water and NaOH solution to maintain particle size stability. After the reaction is stable, the material is prepared to obtain a core with an average particle size D50 of 3.0 μm.

[0115] Step 2: The kernel of step 1 is put into a reactor, and a certain amount of pure water, sodium hydroxide solution (mass percentage concentration is 20.0%) and ammonia solution (mass percentage concentration is 16.4%) are added to the reactor, and stirred evenly under constant temperature conditions to obtain a second bottom liquid with a pH of 12-13 and an ammonia mass concentration of 8.5g / L, and the stirring speed is 370r / min; the second bottom liquid is protected by inert gas, and the metal salt mixed solution, complexing agent and precipitant are added to the second bottom liquid reactor, the reaction temperature is 40-45°C, and the feeding and discharging are continuous. During the reaction process, the pH is controlled to be within the range of 12.3-12.5 and the ammonia concentration fluctuates within the range of 8.5-9g / L by fine-tuning the flow rate of the precipitant and complexing agent, and the kernel of step 2 is continuously added to maintain the particle size stable. After the reaction is stable, the material is prepared to obtain an average particle size D50 of 15.4μm, and the reaction product is post-treated to obtain a chemical formula of Ni 0.88 Co 0.09 Mn 0.03 Precursor of (OH)2.

[0116] (2) Preparation of Class B particles: nickel salt, cobalt salt and manganese salt are prepared into a metal salt solution according to the molar ratio of Ni:Co:Mn=79:12:9, wherein the sum of the metal ion mass concentrations is 120 g / L. Pure water, sodium hydroxide solution (mass percentage concentration of 20.0%) and ammonia solution (mass percentage concentration of 16.4%) were added to the reactor to prepare a bottom liquid with a pH value of 9.2-9.5 and an ammonia concentration of 2.5 g / L; the stirring speed was 340 r / min; an inert gas was passed through the bottom liquid for protection, and the metal salt mixed solution, ammonia solution and NaOH solution were added to the first bottom liquid reactor. The reaction temperature was 45-50 ° C, and the materials were continuously fed and discharged. During the reaction, the flow rate of ammonia solution and NaOH solution was fine-tuned to control the pH to be within the range of 9.1-9.6 and the ammonia concentration to fluctuate within the range of 2.3-2.8 g / L, so as to maintain the particle size stability. After the reaction stabilized, the material was prepared to obtain an average particle size D50 of 3.4 μm. The reaction product was post-processed to obtain a chemical formula of Ni 0.79 Co 0.12 Mn 0.09 Precursor of (OH)2.

[0117] (3) The type A particles and the type B particles are uniformly mixed in a mass ratio of 6.5:3.5 to obtain the high-density positive electrode material precursor.

[0118] Example 2-2 to Example 2-4

[0119] Example 2-2 to Example 2-4: The difference from Example 2-1 is that the mass ratio of the mixture of Class A particles and Class B particles is different. The specific ratio is shown in Table 1.

[0120] Example 3-1 to Example 3-2

[0121] The differences from Example 2-1 are: 1) the Class B particles used are the Class B particles described in Example 1-1, and 2) the mass ratio of the mixture of Class A particles and Class B particles is different. The specific ratio is shown in Table 1.

[0122] Example 4-1 to Example 4-3

[0123] The differences from Example 1-1 are: 1) the preparation method of the Class B particles used is the same as that described in Example 2-1, except that the reaction is stopped when the particle size D50 is 3.38 μm; 2) the mass ratio of the mixture of Class A particles and Class B particles is different, and the specific ratio is shown in Table 1.

[0124] Comparative Example 1-1 to Comparative Example 1-3

[0125] The difference from Example 3-1 is that the mass ratio of the mixture of Class A particles and Class B particles is different. The specific ratio is shown in Table 1.

[0126] Comparative Example 2-1 to Comparative Example 2-2

[0127] The differences from Example 1-1 are: 1) the Class B particles used are the Class B particles described in Example 4-1, and 2) the mass ratio of the mixture of Class A particles and Class B particles is different. The specific ratio is shown in Table 1.

[0128] Comparative Example 3-Comparative Example 5

[0129] Comparative Example 3: The difference from Example 2-1 is that the mass ratio of the mixture of Class A particles and Class B particles is different. The specific ratio is shown in Table 1.

[0130] Comparative Example 4-Comparative Example 5: The difference from Examples 1-6 is that the mass ratio of the mixture of Class A particles and Class B particles is different. The specific ratios are shown in Table 1.

[0131] Among them, the number density distribution diagram of Examples 1-5 is shown in Figure 1, the number ratio of different particle sizes in the number density distribution diagram of Examples 1-5 is shown in Figure 2, and the number density distribution diagram of Example 2-1 is shown in Figure 3. Figure 4 is a number ratio diagram of different particle sizes of Example 2-1; Figure 5 is a number ratio diagram of different particle sizes of Example 3-1; Figure 6 is a number ratio diagram of different particle sizes of Example 4-1; Figure 7 is a number ratio diagram of different particle sizes of Comparative Example 1-1; and Figure 8 is a number ratio diagram of different particle sizes of Comparative Example 2-2.

[0132] The compaction density test method is: Material software and a 300kN controlled electronic pressure testing machine are used to calculate the compaction density. The operation steps are as follows: Place the empty mold on the test bench, pre-press with a certain pressure, record the height at this time as h0, and mark zero; then weigh about 1g of the precursor powder sample, and record the specific mass as m; place the sample in the mold, shake it flat, place it on the test bench, set the test pressure (0.75t), holding time and other parameters, and the test height is h1; finally, according to the area S of the mold (132.665mm 2 The compacted density is calculated from the height h (h = h1 - h0) of the sample after compaction and the mass m. For the same sample, the average of three sets of compacted density measurements is the compacted density of the sample.

[0133] The particle size distribution test method is: using a Mastersizer 3000 instrument to test and obtain the average particle size.

[0134] The operating steps are as follows: first initialize the computer to the light energy between -10 and 10, the laser below 0.00%, ensure that the stirrer is rotating, modify the mode of the sample to be tested on the computer, ultrasonic intensity 80% time 60s, analysis mode Malvern 3000, background measurement duration 6s, sample measurement duration 6s, measurement number 3 times, the sample average value is the particle size of the sample.

[0135] The precursor data obtained in the examples and comparative examples are shown in Table 1, and the corresponding data of the particle size distribution peak are shown in Table 2:

[0136] Table 1 Precursor data obtained from Examples and Comparative Examples

[0137] Table 2 Corresponding data of particle size distribution peaks of various embodiments and comparative examples

[0138] In the precursor product of this embodiment, the ratio of the number of the first type of particles (particle size D < 5 μm) to the number of the second type of particles (particle size D ≥ 5 μm) is (10-40): 1. The ratio of their number ratios is controlled so that the precursors of different particle sizes are within the appropriate number ratio range, and the larger number of small particles has an ideal filling effect on the gaps between the large particles, thereby generally feedback that the positive electrode material precursor has a high compaction density. The positive electrode material is made using it and assembled into a button battery for testing. Under the voltage range of 3.0-4.3V, the first discharge capacity at 1C (1C = 200mA / g) can be greater than 230mAh / g, wherein some particle size distribution test graphs have a bimodal distribution, and the number ratio of the particles corresponding to the first peak to the number ratio of the particles corresponding to the second peak is (10-50): 1, with high compaction density and high small particle number density. The rate performance at 7C / 1C can be greater than 91%, and the high rate performance is excellent.

[0139] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present disclosure, rather than to limit them. Although the present disclosure has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present disclosure. Industrial Applicability

[0140] The present disclosure provides a high-density cathode material precursor and a preparation method thereof, a lithium-ion battery and a lithium battery device, which have broad application prospects in the battery field.

Claims

1. A high-compaction cathode material precursor, characterized in that, It includes a first type of particles with a particle size less than 5 μm and a second type of particles with a particle size greater than or equal to 5 μm; The ratio of the quantity proportion of the first type of particles to the quantity proportion of the second type of particles is (10 - 40):

1.

2. The high-compaction cathode material precursor according to claim 1, wherein The high-compactness cathode material precursor satisfies at least one of the following conditions: (1) The quantity proportion of the first type of particles is 90% - 99.9%, optionally 92 - 98%; (2) The quantity proportion of the second type of particles is 1% - 10%, optionally 5% - 10%; (3) The particle size of the second type of particles is 5 - 30 μm; (4) The ratio of the quantity proportion of the first type of particles to the quantity proportion of the second type of particles is (11.5 - 22.5):1, optionally (13.5 - 18.0):

1.

3. The high-compaction cathode material precursor according to claim 1 or 2, wherein In the particle size distribution test chart of the high-compactness cathode material precursor, there are a first peak and a second peak, and the first peak and the second peak satisfy at least one of the following conditions: (5) The particle size corresponding to the highest quantity proportion of the first peak is located at 1 - 5 μm, optionally 1 - 3 μm; (6) The particle size corresponding to the highest quantity proportion of the second peak is located at 6 - 20 μm, optionally 7 - 15 μm.

4. The high-compaction cathode material precursor according to claim 3, wherein The first peak and the second peak satisfy at least one of the following conditions: (7) The ratio of the quantity proportion of the particles corresponding to the first peak to the quantity proportion of the particles corresponding to the second peak is (10 - 50):1, optionally (10 - 30):1; (8) The ratio of the highest quantity proportion of the first peak to the highest quantity proportion of the second peak is (10 - 40):1, optionally (10 - 20):

1.

5. The high-compaction cathode material precursor according to claim 1 or 2, characterized in that, Satisfy one or more of the following conditions: A. The tap density of the high-compaction cathode material precursor is not less than 3.3 g / cm 3 , optionally not less than 3.6 g / cm 3 ; B. The D50 of the high-compactness cathode material precursor is 8 - 20 μm; C. The specific surface area BET of the high-compaction cathode material precursor is 5-15 m 2 / g; D. The tap density TD of the high-compaction cathode material precursor is not less than 2.3 g / cm 3 ; E. The high-compactness cathode material precursor includes a nickel element-containing compound, optionally nickel cobalt manganese hydroxide.

6. A method for preparing the high-compactness cathode material precursor according to any one of claims 1-5, characterized in that, It includes: Mix two or more types of precursor particles to obtain the high-compactness cathode material precursor.

7. The preparation method of the high-compaction cathode material precursor according to claim 6, wherein The mixing includes: mixing A-type precursor particles and B-type precursor particles to obtain the high-compactness cathode material precursor; The A-type precursor particles and the B-type precursor particles satisfy one or more of the following conditions: (1) The mass ratio of the A-type precursor particles to the B-type precursor particles is (1.5 - 6):1; (2) The D50 of the A-type precursor particles is 12 - 25 μm, optionally 14 - 20 μm; (3) The Span value of the A-type precursor particles is 0.3 - 1.5, optionally 0.3 - 0.5 or 1.0 - 1.5; (4) The D50 of the B-type precursor particles is 1.0 - 8.0 μm, optionally 3.0 - 6.0 μm; (5) The Span value of the B-type precursor particles is 0.4 - 1.5, optionally 0.5 - 0.8 or 1.0 - 1.

5.

8. A high-compaction cathode material, characterized in that, Its raw material includes the high-compactness cathode material precursor according to any one of claims 1 - 6.

9. A battery, characterized in that, It includes the high-compactness cathode material according to claim 8.

10. An electric-related device, characterized in that, It includes the battery according to claim 9.

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