Additives for replenishing lithium or sodium, methods for producing the same, and uses

Abstract

The present invention provides a lithium or sodium replenishment additive, as well as its manufacturing method and use, for batteries. The additive is mainly made of oxalic acid, salt, and catalyst, where the salt includes lithium salt or sodium salt. The particle size distribution concentration of the lithium or sodium replenishment additive satisfies the formula: 1≦(D90-D10) / D50≦100. When the specific surface area of the lithium or sodium replenishment additive is S, the D10, D50, and D90 of S, the lithium or sodium replenishment additive satisfy the formula: 1≦(S / ((D90-D10) / D50))≦100. The provided additive has a low decomposition voltage, a high specific capacity, a small particle size, and a low catalyst usage.

Description

[Technical Field]

[0001] [Cross-reference of related applications] This application claims priority to a Chinese patent application filed with the China National Intellectual Property Office on April 21, 2023, with application number 2023104377951, titled "Additive for supplementing lithium or sodium, method for manufacturing the same, and uses," the entire contents of which are incorporated into this application by reference.

[0002] [Technical field] This disclosure relates to the field of batteries, and more particularly to lithium or sodium supplements, as well as methods for producing the same and their applications. [Background technology]

[0003] In lithium-ion and sodium-ion batteries, during the first charging cycle, an SEI film forms on the surface of the negative electrode, causing irreversible capacity loss of the positive electrode material and affecting the battery's capacity and cycle life. Therefore, replenishing the positive or negative electrode with lithium or sodium can improve the battery's capacity and cycle characteristics. Compared to replenishing the negative electrode with lithium or sodium, replenishing the positive electrode with lithium or sodium is simpler, does not require additional production steps, and only requires adding a lithium or sodium replenisher when homogenizing the positive electrode slurry. Common positive electrode lithium replenishers include Li2O, Li2O2, Li2S, Li3N, Li2NiO2, Li2CuO2, Li2MnO3, Li2C2O4, Li5FeO4, etc., while common positive electrode sodium replenishers include Na2O, Na2O2, Na2S, Na3N, Na2NiO2, Na2CuO 2、This includes Na2C2O4 and Na5FeO4. Currently, commercially available cathode lithium replenishers are mainly Li2NiO2 and Li5FeO4, but cathode sodium replenishers are not yet commercially available. However, Li2NiO2 material has poor stability, requires surface coating, has low lithium replenishment efficiency, and the resulting product, LiNiO2, has low structural stability and generates a large amount of gas at high temperatures. Li5FeO4 releases a large amount of oxygen during the initial delithiation process, oxidizing the electrolyte and causing gas generation by the core, and LiOH tends to remain on the surface during the synthesis process, resulting in gelation when homogenizing the slurry. In addition, these two lithium replenishers have strict synthesis conditions and require strict control of moisture during the synthesis process, resulting in high manufacturing costs. Therefore, it is necessary to develop low-cost lithium and sodium replenishers that leave no residue and are stable in air.

[0004] Lithium oxalate and sodium oxalate are low-cost, stable in air, leave no residue after the first charging cycle, and are acidic lithium and sodium replenishers. However, they have a high decomposition voltage (4.7V), which does not match the voltage of lithium iron phosphate, the currently mainstream ternary cathode material, and therefore are not commercially available. Patent CN114300680A describes a process in which unmodified lithium oxalate is dissolved in water, a cobalt tetroxide quantum dot dispersion is slowly added dropwise to the above solution and mixed uniformly, then a carbon nanotube dispersion is slowly added dropwise to the above solution to obtain a precursor solution. This precursor solution is then atomized using an ultrasonic nebulizer to finally obtain modified lithium oxalate, but the synthesis process is relatively complex. Patent CN114464909 describes a process in which a prepared catalyst is dispersed in a saturated aqueous solution of lithium oxalate, mixed uniformly, then ethanol is slowly added dropwise to the dispersion to precipitate lithium oxalate by recrystallization, and then centrifuged and dried to obtain a composite lithium replenisher material containing lithium oxalate and catalyst. In patent CN110112475A, oxalic acid solution and sodium carbonate solution are prepared separately. The oxalic acid solution is slowly added dropwise to the sodium carbonate solution to form a homogeneous solution. Then, this mixed solution is added dropwise to ethanol to generate a precipitate, which is filtered by suction and dried to obtain the final product, sodium oxalate (Na2C2O4). However, the sodium oxalate particles synthesized by this method are large, approximately 1 μm in size. [Overview of the project]

[0005] This disclosure relates to an additive for replenishing lithium or sodium, It is mainly produced from oxalic acid, salts, and catalysts. The salt includes a lithium salt or a sodium salt. The particle size distribution concentration of the lithium or sodium supplement satisfies the formula: 1 ≤ (D90 - D10) / D50 ≤ 100. When the specific surface area of the additive for replenishing the lithium or sodium is S, S, D10, D50, and D90 of the additive for replenishing the lithium or sodium satisfy the formula: 1 ≦ (S / ((D90 - D10) / D50)) ≦ 100. Provided is an additive for replenishing lithium or sodium, characterized by this.

[0006] In some embodiments, when D50 of the oxalic acid, the salt, the catalyst, and the additive for replenishing the lithium or sodium are respectively Da, Db, Dc, and Dd, Da, Db, Dc, and Dd satisfy the formula: 0.5 ≦ (Da + Db) / (Dc + Dd) ≦ 200.

[0007] In some embodiments, the mass ratio of the oxalic acid, the salt, and the catalyst is 170 - 180:100 - 220:5 - 30.

[0008] In some embodiments, the particle size of the additive for replenishing the lithium or sodium is 0.01 - 50 μm.

[0009] In some embodiments, the pH of the additive for replenishing the lithium or sodium is less than 7.

[0010] In some embodiments, the apparent density of the additive for replenishing the lithium or sodium is 0.5 - 1.5 g / cm 3 is.

[0011] In some embodiments, the catalyst is LiCoO2, LiNi x Co y Mn 1-x-y O2, LiFePO4, LiMn x Fe 1-x O4, LiMn2O4, LiNi 0.5 Mn 1.5O4, a lithium-rich manganese-based cathode, NiO, MnO2, Mn3O4, CoO, Co3O4, Fe3O4, MoO3, WO3, Nb2O5, Mo2C, TaC, SiC, TiN, MoN, WN, TiB2, WB, Ketjen black, conductive carbon super-P, acetylene black, CNT, VGCF, polyaniline, polypyrrole, polythiophene or polypyridine, and at least one of the following: LiNi x Co y Mn 1-x-y In O2, x + y = 1, 0 < x ≤ 1, 0 < y < 1, and in LiMn x Fe 1-x In O4, 0 ≤ x ≤ 1.

[0012] In some embodiments, the lithium salt contains Li2CO3 and / or LiOH.

[0013] In some embodiments, the sodium salt contains at least one of NaOH, Na2CO3, or NaHCO3.

[0014] The present disclosure also provides a method for manufacturing an additive for replenishing lithium or sodium as described above, including the steps of sand milling a uniformly mixed mixture containing oxalic acid, a salt, and a catalyst, and performing spray drying.

[0015] In some embodiments, the sand milling time is 15 to 30 minutes.

[0016] In some embodiments, the material filling efficiency of the sand milling is 40% to 80%.

[0017] In some embodiments, the pressure of the spray drying is 0.2 to 1.0 MPa.

[0018] The present disclosure also provides a cathode material containing an additive for replenishing lithium or sodium.

[0019] This disclosure also provides a lithium-ion or sodium-ion battery comprising the cathode material.

[0020] To more clearly illustrate the technical solutions of the embodiments of this disclosure, the drawings that may be used in the embodiments are briefly introduced below. However, it should be understood that the following drawings are merely illustrative of the embodiments of this disclosure, the dimensional ratios of the drawings do not correspond to the actual scale of the embodiments, and the following drawings show only specific embodiments of this disclosure and should not be construed as limiting the scope. [Brief explanation of the drawing]

[0021] [Figure 1] This is an SEM image (1000x magnification) of an additive that replenishes lithium or sodium according to Example 1 of this disclosure. [Figure 2] This is an SEM image (20,000x magnification) of an additive that replenishes lithium or sodium according to Example 1 of this disclosure. [Figure 3] This figure shows the results of a lithium-ion battery charging test. [Figure 4] This figure shows the results of a charging test of a sodium-ion battery. [Modes for carrying out the invention]

[0022] The advantages of the embodiments in the summary of the invention are described in the portions of the descriptions below that describe embodiments for carrying out the invention, and may be partially apparent from the description or obtained by carrying out some of the embodiments of the present disclosure.

[0023] The technical solutions of this disclosure are described further below through several embodiments with reference to the accompanying drawings.

[0024] To further clarify the purpose, technical solutions, and advantages of this disclosure, the disclosure will be described in more detail below with reference to the drawings and examples. It should be understood that the examples described herein are used solely to illustrate the disclosure and are not intended to limit it. Furthermore, the technical features of the various embodiments of the disclosure described below can be combined with each other, insofar as they do not conflict with each other. Several improvements and modifications can be made without departing from the principles of the embodiments of the disclosure, and these improvements and modifications are also considered to be within the scope of protection of the embodiments of the disclosure.

[0025] This disclosure relates to an additive for replenishing lithium or sodium, It is mainly produced from oxalic acid, salts, and catalysts. The salts include lithium salts or sodium salts. The particle size distribution concentration of the lithium or sodium supplement satisfies the formula: 1 ≤ (D90 - D10) / D50 ≤ 100. The present invention provides a lithium or sodium supplementing additive such that, if S is the specific surface area of ​​the lithium or sodium supplementing additive, then S, D10, D50, and D90 of the lithium or sodium supplementing additive satisfy the formula: 1 ≤ (S / ((D90 - D10) / D50) ≤ 100.

[0026] The lithium or sodium supplementing additives of this disclosure have a low decomposition voltage, high specific capacity, small particle size, and require less catalyst, achieved by carefully selecting raw materials and precisely designing the particle size distribution of the additive, specific surface area, and particle size of the raw materials.

[0027] The particle size distribution concentration of the additive satisfies the formula: 1 ≤ (D90 - D10) / D50 ≤ 100. If the concentration is too high, the D90 of the material becomes too large, resulting in many large particles. As a result, contact with the catalyst decreases, and the capacity of the material decreases. If the concentration is too low, the particle size of the material becomes too small, causing side reactions with the electrolyte, which in turn reduces the capacity and cycle characteristics of the battery.

[0028] If the catalyst particle size is too small and the specific surface area is too large, gel formation is likely to occur during the homogenization process of the cathode slurry. Conversely, if the additive particle size is too small, it is disadvantageous for uniformly mixing the additive with the cathode material. If the specific surface area of ​​the additive is S, then S, the additive's D10, D50, and D90 satisfy the equation: 1 ≤ (S / ((D90 - D10) / D50) ≤ 100. If the parameters are too large, it indicates that the specific surface area is too large and the particle size distribution is too concentrated, which is not helpful for mixing the additive with the cathode material and homogenizing the slurry. If the parameters are too small, it indicates that the specific surface area is too small, the particle size distribution is too concentrated, and the particle size of the material is too large, resulting in a decrease in capacity.

[0029] In some embodiments, if the oxalic acid, salt, catalyst, and lithium or sodium-replenishing additive D50 are Da, Db, Dc, and Dd, respectively, then Da, Db, Dc, and Dd satisfy the formula: 0.5 ≤ (Da + Db) / (Dc + Dd) ≤ 200.

[0030] If the D50 of oxalic acid, salt, catalyst, and additive are Da, Db, Dc, and Dd, respectively, then Da, Db, Dc, and Dd satisfy the equation: 0.5 ≤ (Da + Db) / (Dc + Dd) ≤ 200. This equation must be satisfied between the raw materials and the finished product. If this parameter is too low, it indicates that the particle size of the oxalic acid and lithium salt used is too small, and the particle size of the catalyst and synthesized additive is too large. This does not help with uniform mixing during the sand milling process. On the other hand, the large particle size of the catalyst results in a low catalytic effect, the large particle size of the additive results in long insertion and release pathways for lithium ions, poor rate characteristics of the material, and consequently, insufficient utilization of capacity. If this parameter is too high, it indicates that the particle size of the oxalic acid and salt used is too large, and the particle size of the catalyst and additive is too small. This does not help with uniform mixing during the sand milling process.

[0031] In some embodiments, the mass ratio of oxalic acid, salt, and catalyst is 170-180:100-220:5-30 (for example, 170:220:5, 172:200:10, 174:180:14, 176:160:20, 178:140:25, or 180:100:30).

[0032] In some embodiments, the particle size of the lithium or sodium supplement is 0.01 to 50 μm (for example, 0.01 μm, 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, or 50 μm).

[0033] In some embodiments, the pH of the lithium or sodium-replenishing additive is less than 7.

[0034] In some embodiments, the apparent density of the lithium or sodium supplement is 0.5 to 1.5 g / cm³. 3 (For example, 0.5 g / cm³) 3 , 0.7 g / cm³ 3 , 0.9 g / cm³ 3 , 1.1 g / cm³ 3 1.3 g / cm³ 3 , or 1.5 g / cm³ 3 )

[0035] In some embodiments, the catalyst is LiCoO2, LiNi x Co y Mn 1-x-y O2, LiFePO4, LiMn x Fe 1-x O4, LiMn2O4, LiNi 0.5 Mn 1.5O4, lithium-rich manganese cathode, NiO, MnO2, Mn3O4, CoO, Co3O4, Fe3O4, MoO3, WO3, Nb2O5, Mo2C, TaC, SiC, TiN, MoN, WN, TiB2, WB, Ketjenblack, conductive carbon super-P, acetylene black, CNT, VGCF, polyaniline, polypyrrole, polythiophene, or polypyridine, comprising at least one of these, LiNi x Co y Mn 1-x-y In O2, x+y=1, 0 <x≦1、0<y<1であり、LiMn x Fe 1-x In O4, 0 ≤ x ≤ 1.

[0036] In some embodiments, the lithium salt includes Li2CO3 and / or LiOH.

[0037] In some embodiments, the sodium salt comprises at least one of NaOH, Na2CO3, or NaHCO3.

[0038] This disclosure also, The present invention relates to a method for producing an additive that replenishes lithium or sodium, comprising the steps of uniformly mixing a mixture containing oxalic acid, a salt, and a catalyst, sand milling the mixture, and spray drying it.

[0039] The method for producing lithium or sodium supplemental additives described herein is simple and easy to implement, and has significant practical implications for accelerating the commercialization of lithium oxalate and sodium oxalate. By sand milling oxalic acid, lithium salt (sodium salt), and catalyst, and then spray drying, lithium or sodium supplemental additives with excellent performance can be obtained. All additives synthesized by this method are nanoscale, are very uniformly mixed with the catalyst, have very low manufacturing costs, and are easy to mass-produce and commercialize.

[0040] In some embodiments, the sand milling time is 15 to 30 minutes (for example, 15 minutes, 20 minutes, 25 minutes, or 30 minutes).

[0041] In some embodiments, the material filling efficiency of sand milling is 40% to 80% (e.g., 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%).

[0042] In some embodiments, the spray drying pressure is 0.2 to 1.0 MPa (e.g., 0.2 MPa, 0.4 MPa, 0.6 MPa, 0.8 MPa, or 1.0 MPa).

[0043] In some embodiments, baking is performed after spray drying.

[0044] In some embodiments, the baking temperature is 95 to 150°C (for example, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, or 150°C).

[0045] In some embodiments, the baking time is 5 to 15 hours (for example, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, or 15 hours).

[0046] This disclosure also relates to cathode materials, including additives that supplement lithium or sodium.

[0047] This disclosure also relates to lithium-ion or sodium-ion batteries, including cathode materials. [Examples]

[0048] The following are non-limiting representative embodiments of this disclosure.

[0049] Example 1 The method for producing a lithium-replenishing additive according to this embodiment includes the following steps. 1. Dissolve 173g of oxalic acid dihydrate (H2C2O4·2H2O), 115g of lithium hydroxide monohydrate (LiOH·H2O), 7.8g of Co3O4, and 7.8g of KB (Ketjenbrak) in 400g of water and stir continuously for 4 hours. 2. After the reaction was complete, the solution was added to the sand mill and sand milled for 23 minutes to achieve a material filling efficiency of 60%. 3. The sand-milled material was placed in a spray dryer and sprayed at a pressure of 0.2 MPa. 4. The sprayed material was baked in a 100°C oven for 10 hours to obtain the final product. The additive obtained in Example 1 was observed using a scanning electron microscope. Figure 1 is a low-magnification electron microscope image, showing that Pa1 is 17.65 μm, Pa2 is 12.81 μm, Pa3 is 12.58 μm, Pa4 is 8.293 μm, Pa5 is 5.362 μm, and Pa6 is 10.44 μm. Figure 2 is a high-magnification electron microscope image, showing that Pa1 is 695.3 nm, Pa2 is 756 nm, Pa3 is 195.0 nm, Pa4 is 443.4 nm, Pa5 is 1.263 μm, and Pa6 is 273.8 nm. As can be seen from Figures 1 and 2, the additive has a spherical appearance, the primary particle size is approximately 400 nm, and it is a nanomaterial.

[0050] Example 2 The method for producing a lithium-replenishing additive according to this embodiment includes the following steps. 1. Dissolve 170g of oxalic acid dihydrate (H2C2O4·2H2O), 110g of lithium hydroxide monohydrate (LiOH·H2O), 45g of Co3O, and 5g of KB (Ketjenbrak) in 400g of water and stir continuously for 4 hours. 2. After the reaction was complete, the solution was added to the sand mill and sand milled for 15 minutes to achieve a material filling efficiency of 40%. 3. The sand-milled material was placed in a spray dryer and sprayed at a pressure of 0.2 MPa. 4. The sprayed material was baked in a 100°C oven for 10 hours to obtain the final product.

[0051] Example 3 The method for producing a lithium-replenishing additive according to this embodiment includes the following steps. 1. Dissolve 180g of oxalic acid dihydrate (H2C2O4·2H2O), 120g of lithium hydroxide monohydrate (LiOH·H2O), 10g of Co3O4, and 10g of KB (Ketjenbrak) in 400g of water and stir continuously for 4 hours. 2. After the reaction was complete, the solution was added to the sand mill and sand milled for 30 minutes to achieve a material filling efficiency of 80%. 3. The sand-milled material was placed in a spray dryer and sprayed at a pressure of 0.2 MPa. 4. The sprayed material was baked in a 100°C oven for 10 hours to obtain the final product.

[0052] Example 4 The method for producing a lithium-replenishing additive according to this embodiment includes the following steps. 1. Dissolve 176g of oxalic acid dihydrate (H2C2O4·2H2O), 118g of lithium hydroxide monohydrate (LiOH·H2O), 48.5g of Co3O, and 8.5g of KB (Ketjenbrak) in 400g of water and stir continuously for 4 hours. 2. After the reaction was complete, the solution was added to the sand mill and sand milled for 26 minutes to achieve a material filling efficiency of 75%. 3. The sand-milled material was placed in a spray dryer and sprayed at a pressure of 0.2 MPa. 4. The sprayed material was baked in a 100°C oven for 10 hours to obtain the final product.

[0053] Example 5 The method for producing a lithium-replenishing additive according to this embodiment includes the following steps. 1. Dissolve 173g of oxalic acid dihydrate (H2C2O4·2H2O), 115g of lithium hydroxide monohydrate (LiOH·H2O), 7.8g of polyaniline, and 7.8g of LiCoO2 in 400g of water and stir continuously for 4 hours. Steps 2-4 were the same as in Example 1.

[0054] Example 6 The method for producing a lithium-replenishing additive according to this embodiment includes the following steps. 1. Dissolve 173g of oxalic acid dihydrate (H2C2O4·2H2O), 115g of lithium hydroxide monohydrate (LiOH·H2O), 7.8g of WN, and 7.8g of Fe3O4 in 400g of water and stir continuously for 4 hours. Steps 2-4 were the same as in Example 1.

[0055] Example 7 The method for producing the sodium-replenishing additive according to this embodiment includes the following steps. 1. Dissolve 173g of oxalic acid dihydrate (H2C2O4·2H2O), 110g of NaOH, 7.8g of Co3O4, and 7.8g of KB (Ketjenblack) in 400g of water and stir continuously for 4 hours. Steps 2-4 were the same as in Example 1.

[0056] Comparative Example 1 Compared to Example 1, this method differs in that steps 2 and 3 are omitted.

[0057] Comparative Example 2 Compared to Example 7, this method differs in that steps 2 and 3 are omitted.

[0058] Experimental Example 1 The particle size distribution, specific surface area, and pH of the obtained additives were measured using a laser particle size analyzer and a pH meter, and the results are shown in Tables 1 and 2. In the examples, the D50 of the additives was 5.25 to 8.38 μm, and the pH was 6.54 to 6.85. Since the material is acidic, it does not affect the homogenization of the cathode material slurry. The specific surface area was 37 to 57 m². 2 The value is / g. The additives in the comparative examples were not subjected to sand milling or spraying, and the materials did not meet the particle size requirements specified in this disclosure and had a small specific surface area.

[0059] [Table 1]

[0060] [Table 2]

[0061] Experimental Example 2 The additives obtained in Examples 1-6, Comparative Examples 1 and 3, the conductive agent SP (carbon black), and the binder PVDF (polyvinylidene fluoride) were mixed in a mass ratio of 8:1:1 to produce a positive electrode slurry. This slurry was coated onto aluminum foil to form a positive electrode plate. A lithium-ion battery was assembled using metallic lithium as the negative electrode plate, Celgard 2400 polypropylene microporous membrane as the separator, and LiPF6 (lithium hexafluoride phosphate) / EC (ethylene carbonate)-DMC (dimethyl carbonate) as the electrolyte. Each assembled lithium-ion battery was subjected to a charging test. The results of the charging tests are shown in Figure 3.

[0062] The additives obtained in Example 7 and Comparative Example 2, the conductive agent SP (carbon black), and the binder PVDF (polyvinylidene fluoride) were mixed in a mass ratio of 8:1:1 to produce a positive electrode slurry. This slurry was coated onto aluminum foil to form a positive electrode plate. A sodium metal was used as the negative electrode plate, a Celgard 2400 polypropylene microporous membrane as the separator, and NaPF6 (sodium hexafluoride phosphate) / EC (ethylene carbonate)-DMC (dimethyl carbonate) as the electrolyte to assemble a sodium-ion battery. Each assembled sodium-ion battery was subjected to a charging test. The results of the charging test are shown in Figure 4.

[0063] The lithium oxalate produced in Example 1 had a low decomposition voltage of 4.2-4.3V and a specific capacity of 520mAh / g. The lithium oxalate produced in Comparative Example 1 had a high decomposition voltage of 4.3-4.5V and a specific capacity of 438mAh / g. The reason for the superior performance of Example 1 is that the material is nanoscale, and the lithium oxalate and catalyst are completely and uniformly mixed, which helps the catalyst lower the decomposition voltage of lithium oxalate and increase its capacity.

[0064] The sodium oxalate produced in Example 7 had a low decomposition voltage of 4.2-4.3V and a specific capacity of 400mAh / g. The sodium oxalate produced in Comparative Example 2 had a high decomposition voltage of 4.4-4.7V and a specific capacity of 249mAh / g. The reason for the superior performance of Example 2 is that the material is nanoscale, and the sodium oxalate and catalyst are completely and uniformly mixed, which helps the catalyst lower the decomposition voltage of sodium oxalate and increase its capacity. [Industrial applicability]

[0065] In summary, this disclosure provides lithium or sodium supplementing additives, methods for producing the same, and applications. These lithium or sodium supplementing additives have a low decomposition voltage, high specific capacity, small particle size, and require little catalyst. The production method is simple and easy to operate, and the resulting lithium or sodium supplementing additives have excellent performance. All additives synthesized by this method are nanometer-sized, very uniformly mixed with the catalyst, have very low production costs, and are easy to mass-produce.

Claims

1. An additive for supplementing lithium or sodium in a positive electrode material, The reaction product of oxalic acid, salt, and catalyst, The salt includes a lithium salt or a sodium salt. The particle size distribution concentration of the lithium or sodium supplement satisfies the formula: 1 ≤ (D90 - D10) / D50 ≤ 100, and the units of D10, D50 and D90 are μm. If S is the specific surface area of ​​the lithium or sodium-replenishing additive, then S, D10, D50, and D90 of the lithium or sodium-replenishing additive satisfy the formula: 1 ≤ (S / ((D90 - D10) / D50) ≤ 100, and the unit of S is m² / g. The additive for supplementing lithium or sodium has D50 of 1 μm to 50 μm, The catalysts include LiCoO₂, LiNi xCoyMn 1-xyO₂, LiFePO₄, LiMn xFe 1-xO₄, LiMn₂O₄, LiNi 0.5Mn 1.5O₄, lithium-rich manganese cathodes, NiO, MnO₂, Mn₃O₄, CoO, Co₃O₄, Fe₃O₄, MoO₃, WO₃, Nb₂O₅, Mo₂C, TaC, SiC, TiN, MoN, WN, and TiB₂. An additive for supplementing lithium or sodium in a positive electrode material, characterized by comprising at least one of WB, Ketjenblack, conductive carbon, acetylene black, CNT, VGCF, polyaniline, polypyrrole, polythiophene, and polypyridine, wherein in the LiNi x Co y Mn 1-xy O 2, x + y = 1, 0 < x ≤ 1, and 0 < y < 1, and in the LiMn x Fe 1-x O 4, 0 ≤ x ≤ 1.

2. The lithium or sodium supplement additive according to claim 1, characterized in that, if D50 of the oxalic acid, the salt, the catalyst, and the lithium or sodium supplement additive are Da, Db, Dc, and Dd, respectively, then Da, Db, Dc, and Dd satisfy the formula: 0.5 ≤ (Da + Db) / (Dc + Dd) ≤ 200.

3. The lithium or sodium supplement additive according to claim 1, characterized in that the mass ratio of the oxalic acid, the salt, and the catalyst is 170-180:100-220:5-30.

4. The lithium or sodium supplement additive according to claim 1, characterized in that the pH is less than 7.

5. Apparent density is 0.5–1.5 g / cm³ 3 The additive for replenishing lithium or sodium according to claim 1, characterized in that it is the same.

6. The lithium salt is Li 2 CO 3 An additive for replenishing lithium or sodium according to claim 1, characterized by comprising and / or LiOH.

7. The aforementioned sodium salt is NaOH, Na 2 CO 3 , or NaHCO 3 An additive for replenishing lithium or sodium according to claim 1, characterized by comprising at least one of the following.

8. A method for producing an additive that replenishes lithium or sodium according to any one of claims 1 to 7, characterized by comprising the steps of uniformly mixing a mixture containing oxalic acid, a salt, and a catalyst, sand milling the mixture, and spray drying it.

9. The method for producing an additive for replenishing lithium or sodium according to claim 8, characterized in that the sand milling time is 15 to 30 minutes.

10. The method for producing an additive for replenishing lithium or sodium according to claim 8, characterized in that the material filling efficiency of the sand milling is 40% to 80%.

11. The method for producing an additive for replenishing lithium or sodium according to claim 8, characterized in that the pressure of the spray drying is 0.2 to 1.0 MPa.

12. A positive electrode material characterized by comprising an additive for replenishing lithium or sodium as described in any one of claims 1 to 7.

13. A lithium-ion or sodium-ion battery characterized by comprising the positive electrode material described in claim 12.

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