A lithium or sodium supplement additive, a preparation method and application thereof

Abstract

The present application relates to the field of battery, and particularly relates to a lithium or sodium supplementing additive and a preparation method and application thereof.The additive is mainly made of oxalic acid, salt and catalyst; the salt comprises lithium salt or sodium salt; the particle size distribution concentration degree of the lithium or sodium supplementing additive satisfies the following formula: 1 <= (D90-D10) / D50 <= 100; the specific surface area of the lithium or sodium supplementing additive is S, and S and D10, D50 and D90 of the lithium or sodium supplementing additive satisfy the following formula: 1 <= S / ((D90-D10) / D50) <= 100.The additive has low decomposition voltage, high specific capacity, small particle size and low catalyst consumption.

Description

Technical Field

[0001] This invention relates to the field of batteries, and more specifically, to an additive for supplementing lithium or sodium, its preparation method, and its application. Background Technology

[0002] During the first week of charging, lithium-ion and sodium-ion batteries develop an SEI film on the negative electrode surface, causing irreversible capacity loss in the positive electrode material, thus affecting battery capacity and cycle life. Therefore, battery capacity and cycle performance can be improved by adding lithium or sodium to the positive or negative electrode. Adding lithium and sodium to the positive electrode is simpler and easier than adding lithium and sodium to the negative electrode, requiring no additional production steps; it only requires adding a lithium or sodium supplement during the positive electrode homogenization process. Common positive electrode lithium supplements include Li₂O, Li₂O₂, Li₂S, Li₃N, Li₂NiO₂, Li₂CuO₂, Li₂MnO₃, Li₂C₂O₄, and Li₅FeO₄, while common positive electrode sodium supplements include Na₂O, Na₂O₂, Na₂S, Na₃N, Na₂NiO₂, and Na₂CuO. 2、 Na2C2O4, Na5FeO4, etc. Currently, the commercially available cathode lithium supplementers are mainly Li2NiO2 and Li5FeO4, while cathode sodium supplementers are not yet commercially available. However, Li2NiO2 material has poor stability, requires surface coating, has low lithium supplementation efficiency, and the product is LiNiO2 with poor structural stability and severe gas generation at high temperatures. Li5FeO4 releases a large amount of oxygen during the initial delithiation process, oxidizing the electrolyte and causing gas generation in the cell. LiOH residues are easily left on the surface during synthesis, causing a gel-like consistency in the homogenate. Furthermore, the synthesis conditions for these two lithium supplementers are demanding, requiring strict control of moisture during the synthesis process, resulting in high manufacturing costs. Therefore, developing a low-cost, residue-free, air-stable lithium and sodium supplementer is imperative.

[0003] Lithium oxalate and sodium oxalate are low-cost, air-stable, residue-free, and acidic lithium and sodium replenishing agents, but their high decomposition voltage (4.7V) does not match the voltage of current mainstream ternary cathode materials and lithium iron phosphate, so they have not been commercialized. Patent CN 114300680 A dissolves unmodified lithium oxalate in water, then slowly adds a cobalt tetroxide quantum dot dispersion to the solution. After stirring until homogeneous, a carbon nanotube dispersion is slowly added to the solution to obtain a precursor solution. The precursor solution is then atomized using an ultrasonic atomizer to finally obtain modified lithium oxalate. The synthesis process is relatively complex. Patent CN114464909 disperses the prepared catalyst in a saturated aqueous solution of lithium oxalate. After stirring until homogeneous, ethanol is slowly added to the dispersion. Lithium oxalate is precipitated by recrystallization, followed by centrifugation and drying to obtain a composite lithium supplement material containing lithium oxalate and the catalyst. Patent CN110112475A prepares oxalic acid and sodium carbonate solutions separately, then slowly adds the oxalic acid solution to the sodium carbonate solution to form a homogeneous solution. The mixed solution is then added to ethanol to generate a precipitate, which is filtered and dried to obtain sodium oxalate (Na2C2O4) as the final product. However, the sodium oxalate particles synthesized by this method are relatively large, around 1 μm in size.

[0004] In view of this, the present invention is hereby proposed. Summary of the Invention

[0005] One aspect of the present invention relates to an additive for supplementing lithium or sodium, which is mainly composed of oxalic acid, salt and catalyst;

[0006] The salts include lithium salts or sodium salts;

[0007] The particle size distribution concentration of the lithium or sodium supplementation additive satisfies the following formula:

[0008] 1≤(D90-D10) / D50≤100;

[0009] The specific surface area of ​​the lithium or sodium supplement is S, and S satisfies the following formula with respect to the D10, D50, and D90 of the lithium or sodium supplement:

[0010] 1≤S / ((D90-D10) / D50)≤100.

[0011] The lithium or sodium supplement additives described above have low decomposition voltage, high specific capacity, small particle size, and require less catalyst.

[0012] Another aspect of the present invention relates to a method for preparing the aforementioned lithium or sodium supplementing additive, comprising the following steps:

[0013] The mixture containing oxalic acid, salt, and catalyst is mixed thoroughly and then subjected to sand milling and spray drying.

[0014] The method for preparing the lithium or sodium supplement additive is simple, easy to operate, and yields additives with excellent performance. The additives synthesized by this method are all nanoscale and are mixed very uniformly with the catalyst. The manufacturing cost is extremely low, making it easy to mass-produce and commercialize.

[0015] Another aspect of the invention relates to a cathode material comprising the aforementioned lithium- or sodium-supplementing additives.

[0016] Another aspect of the present invention relates to a lithium-ion or sodium-ion battery comprising the aforementioned positive electrode material.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0018] (1) The lithium or sodium supplementation additive provided by the present invention has strictly selected the raw materials and carefully designed the particle size distribution, specific surface area and particle size of the additive, so that the additive has low decomposition voltage, high specific capacity, small particle size and low amount of catalyst.

[0019] (2) The method for preparing lithium or sodium supplement additives provided by the present invention is simple and easy to operate. Oxalic acid, lithium salt (sodium salt) and catalyst are sand-milled and spray-dried to obtain high-performance lithium or sodium supplement additives. The additives synthesized by this method are all nanoscale and are mixed very evenly with the catalyst. The manufacturing cost is extremely low and it is easy to mass-produce and commercialize. Attached Figure Description

[0020] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0021] Figure 1 SEM image (1000x) of the lithium or sodium supplement additive provided in Example 1 of the present invention.

[0022] Figure 2 SEM image (20000x) of the lithium or sodium supplement additive provided in Example 1 of the present invention.

[0023] Figure 3 Figure showing the results of a lithium-ion battery charging test.

[0024] Figure 4 Figure showing the results of a sodium-ion battery charging test. Detailed Implementation

[0025] The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0026] One aspect of the present invention relates to an additive for supplementing lithium or sodium, which is mainly composed of oxalic acid, salt and catalyst;

[0027] The salts include lithium salts or sodium salts;

[0028] The particle size distribution concentration of the lithium or sodium supplementation additive satisfies the following formula:

[0029] 1≤(D90-D10) / D50≤100;

[0030] The specific surface area of ​​the lithium or sodium supplement is S, and S satisfies the following formula with respect to the D10, D50, and D90 of the lithium or sodium supplement:

[0031] 1≤S / ((D90-D10) / D50)≤100.

[0032] The lithium or sodium supplement additives described herein employ strict selection of raw materials and meticulous design of the additive's particle size distribution, specific surface area, and raw material particle size, resulting in low decomposition voltage, high specific capacity, small particle size, and low catalyst dosage.

[0033] The particle size distribution concentration of the additive satisfies the following formula: 1≤(D90-D10) / D50≤100. If the concentration is too high, the material D90 will be too large, and there will be too many large particles, resulting in less contact with the catalyst and low material capacity utilization. If the concentration is too low, the material particles will be too small, which will cause side reactions with the electrolyte, resulting in a decrease in battery capacity and cycle performance.

[0034] Small catalyst particle size results in an excessively large specific surface area, making gelation during the cathode homogenization process more likely. Insufficiently small additive particle size hinders uniform mixing between the additive and the cathode material. The specific surface area S of the additive, along with its corresponding D10, D50, and D90 values, satisfies the following formula: 1 ≤ S / ((D90-D10) / D50) ≤ 100. A parameter that is too large indicates an excessively large specific surface area and low particle size distribution, which is detrimental to mixing and homogenization of the additive and cathode material. Conversely, a parameter that is too small indicates an excessively small specific surface area and high particle size distribution, resulting in larger particle size and lower capacity utilization.

[0035] Preferably, the D50 of the oxalic acid, the salt, the catalyst, and the lithium or sodium supplementation additive are Da, Db, Dc, and Dd, respectively, and Da, Db, Dc, and Dd satisfy the following formula:

[0036] 0.5≤(Da+Db) / (Dc+Dd)≤200.

[0037] The D50 values ​​for oxalic acid, lithium salt, catalyst, and additives are Da, Db, Dc, and Dd, respectively. Da, Db, Dc, and Dd satisfy the following formula: 0.5 ≤ (Da + Db) / (Dc + Dd) ≤ 200. This formula must be satisfied between raw materials and finished products. A lower parameter indicates that the particle size of the oxalic acid and lithium salt used is small, while the particle size of the catalyst and synthesized additives is large. This is detrimental to uniform mixing during the milling process. Furthermore, large catalyst particle size results in poor catalytic effect, and large additive particle size leads to longer lithium ion insertion and extraction paths, resulting in poor material rate performance and insufficient capacity utilization. A higher parameter indicates that the particle size of the oxalic acid and salt used is large, while the particle size of the catalyst and additives is small, which is also detrimental to uniform mixing during the milling process.

[0038] Preferably, the mass ratio of the oxalic acid, the salt, and the catalyst is 170-180:100-220:5-30 (e.g., 170:220:5, 172:200:10, 174:180:14, 176:160:20, 178:140:25, or 180:100:30).

[0039] Preferably, the particle size of the lithium or sodium supplement is 0.01~50μm (e.g. 0.01μm, 0.05μm, 0.1μm, 0.5μm, 1μm, 5μm, 10μm, 15μm, 20μm, 25μm, 30μm, 35μm, 40μm, 45μm or 50μm).

[0040] Preferably, the pH of the lithium or sodium supplement is <7.

[0041] Preferably, the loose packing density of the lithium or sodium supplement is 0.5~1.5 g / cm³. 3(e.g., 0.5 g / cm 3 , 0.7 g / cm 3 , 0.9 g / cm 3 , 1.1 g / cm 3 , 1.3 g / cm 3 or 1.5 g / cm 3 ).

[0042] Preferably, the catalyst includes at least one of: LiCoO2, LiNi x Co y Mn 1-x-y O2, LiFePO4, LiMn x Fe 1-x O4, LiMn2O4, LiNi 0.5 Mn 1.5 O4, 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; in the LiNi x Co y Mn 1-x-y O2, x + y = 1, 0 < x ≤ 1, 0 < y < 1; in the LiMn x Fe 1-x O4, 0 ≤ x ≤ 1.

[0043] Preferably, the lithium salt includes: Li2CO3 and / or LiOH.

[0044] Preferably, the sodium salt includes at least one of: NaOH, Na2CO3 or NaHCO3.

[0045] Another aspect of the present invention also relates to a preparation method of the lithium or sodium supplement additive, comprising the following steps:

[0046] Mix a mixed solution containing oxalic acid, salt and catalyst, and then perform sand grinding and spray drying.

[0047] The preparation method of the lithium or sodium supplement additive is simple and easy to implement, and has important practical significance for accelerating the commercialization of lithium oxalate and sodium oxalate; by performing sand grinding and spray drying on oxalic acid, lithium salt (sodium salt) and catalyst, a lithium or sodium supplement additive with excellent performance can be obtained; the additives synthesized by this method are all nanoscale, and are mixed very evenly with the catalyst, with extremely low manufacturing cost, and are easy to mass-produce and commercialize.

[0048] Preferably, the grinding time is 15 to 30 minutes (e.g., 15 minutes, 20 minutes, 25 minutes or 30 minutes).

[0049] Preferably, the material filling efficiency of the mill is 40% to 80% (e.g., 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%).

[0050] Preferably, the spray drying pressure is 0.2~1.0 MPa (e.g. 0.2 MPa, 0.4 MPa, 0.6 MPa, 0.8 MPa or 1.0 MPa).

[0051] Preferably, the spray drying is followed by drying.

[0052] Preferably, the drying temperature is 95~150℃ (e.g., 95℃, 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃ or 150℃).

[0053] Preferably, the drying time is 5 to 15 hours (e.g., 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours or 15 hours).

[0054] Another aspect of the invention relates to a cathode material comprising the aforementioned lithium- or sodium-supplementing additives.

[0055] Another aspect of the present invention relates to a lithium-ion or sodium-ion battery comprising the aforementioned positive electrode material.

[0056] The embodiments of the present invention will now be described in detail with reference to specific examples and comparative examples.

[0057] Example 1

[0058] The method for preparing the lithium-supplementing additive provided in this embodiment includes the following steps:

[0059] 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 (Ketjen Black) in 400g of water and stir continuously for 4 hours;

[0060] 2. After the reaction is complete, add the solution to a sand mill for sand milling for 23 minutes, with a material filling efficiency of 60%.

[0061] 3. Add the milled material to the spray dryer for spraying at a pressure of 0.2 MPa;

[0062] 4. Dry the sprayed material in a 100℃ oven for 10 hours to obtain the final product.

[0063] The additive obtained in Example 1 was observed using a scanning electron microscope. Figure 1 This is a low-magnification electron microscope image. Figure 1 In the above, Pa1 equals 17.65 μm, Pa2 equals 12.81 μm, Pa3 equals 12.58 μm, Pa4 equals 8.293 μm, Pa5 equals 5.362 μm, and Pa6 equals 10.44 μm; Figure 2 This is a high-magnification electron microscope image. Figure 2 In the diagram, Pa1 equals 695.3 nm, Pa2 equals 756 nm, Pa3 equals 195.0 nm, Pa4 equals 443.4 nm, Pa5 equals 1.263 μm, and Pa6 equals 273.8 nm. (The remaining text appears to be a fragment and doesn't translate directly.) Figure 1 and Figure 2 It can be seen that the additive has a spherical morphology and a primary particle size of about 400 nm, which is a nanomaterial.

[0064] Example 2

[0065] The method for preparing the lithium-supplementing additive provided in this embodiment includes the following steps:

[0066] 1. Dissolve 170g of oxalic acid dihydrate (H2C2O4·2H2O), 110g of lithium hydroxide monohydrate (LiOH·H2O), 5g of Co3O4, and 5g of KB (Ketjen Black) in 400g of water and stir continuously for 4 hours;

[0067] 2. After the reaction is complete, add the solution to a sand mill for sand milling for 15 minutes, with a material filling efficiency of 40%.

[0068] 3. Add the milled material to the spray dryer for spraying at a pressure of 0.2 MPa;

[0069] 4. Dry the sprayed material in a 100℃ oven for 10 hours to obtain the final product.

[0070] Example 3

[0071] The method for preparing the lithium-supplementing additive provided in this embodiment includes the following steps:

[0072] 1. Dissolve 180g of oxalic acid dihydrate (H2C2O4·2H2O), 120g of lithium hydroxide monohydrate (LiOH·H2O), 10g of Co3O4, and 10g of KB (Ketjen Black) in 400g of water and stir continuously for 4 hours;

[0073] 2. After the reaction is complete, add the solution to a sand mill for sand milling for 30 minutes, with a material filling efficiency of 80%.

[0074] 3. Add the milled material to the spray dryer for spraying at a pressure of 0.2 MPa;

[0075] 4. Dry the sprayed material in a 100℃ oven for 10 hours to obtain the final product.

[0076] Example 4

[0077] The method for preparing the lithium-supplementing additive provided in this embodiment includes the following steps:

[0078] 1. Dissolve 176g of oxalic acid dihydrate (H2C2O4·2H2O), 118g of lithium hydroxide monohydrate (LiOH·H2O), 8.5g of Co3O4, and 8.5g of KB (Ketjen Black) in 400g of water and stir continuously for 4 hours;

[0079] 2. After the reaction is complete, the solution is added to a sand mill for sand milling for 26 minutes, with a material filling efficiency of 75%.

[0080] 3. Add the milled material to the spray dryer for spraying at a pressure of 0.2 MPa;

[0081] 4. Dry the sprayed material in a 100℃ oven for 10 hours to obtain the final product.

[0082] Example 5

[0083] The method for preparing the lithium-supplementing additive provided in this embodiment includes the following steps:

[0084] 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;

[0085] 2-4, Same as Example 1.

[0086] Example 6

[0087] The method for preparing the lithium-supplementing additive provided in this embodiment includes the following steps:

[0088] 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;

[0089] 2-4, Same as Example 1.

[0090] Example 7

[0091] The method for preparing the sodium-supplementing additive provided in this embodiment includes the following steps:

[0092] 1. Dissolve 173g of oxalic acid dihydrate (H2C2O4·2H2O), 110g of NaOH, 7.8g of Co3O4, and 7.8g of KB (Ketjen Black) in 400g of water and stir continuously for 4 hours;

[0093] 2-4, Same as Example 1.

[0094] Comparative Example 1

[0095] The only difference from Example 1 is that steps 2 and 3 are omitted.

[0096] Comparative Example 2

[0097] The only difference from Example 7 is that steps 2 and 3 are omitted.

[0098] Experimental Example 1

[0099] The particle size distribution, specific surface area, and pH of the obtained additives were tested using a laser particle size analyzer and a pH meter. The results are shown in Tables 1 and 2. The D50 of the additives in the examples ranged from 5.25 to 8.38 μm, and the pH ranged from 6.54 to 6.85. The material was acidic; therefore, it would not affect the homogenization of the cathode material. The specific surface area was 37–57 m². 2 / g. The additives in the comparative example were not milled or sprayed, and the particle size of the material did not meet the conditions defined in this invention, resulting in a small specific surface area.

[0100] Table 1

[0101]

[0102] Table 2

[0103]

[0104] Experiment Example 2

[0105] The additives obtained in Examples 1-6, Comparative Examples 1 and 3 were mixed with conductive agent SP (carbon black) and binder PVDF (polyvinylidene fluoride) at a mass ratio of 8:1:1 to form a positive electrode slurry. This slurry was then coated onto aluminum foil to form a positive electrode sheet. Lithium metal was used as the negative electrode sheet, a Celgard 2400 microporous polypropylene membrane was used as the separator, and LiPF6 (lithium hexafluorophosphate) / EC (ethylene carbonate)-DMC (dimethyl carbonate) was used as the electrolyte to assemble lithium-ion batteries. Charging tests were performed on the assembled lithium-ion batteries, and the results are as follows: Figure 3 As shown.

[0106] The additives obtained in Example 7 and Comparative Example 2 were mixed with conductive agent SP (carbon black) and binder PVDF (polyvinylidene fluoride) at a mass ratio of 8:1:1 to form a positive electrode slurry. This slurry was then coated onto aluminum foil to form a positive electrode sheet. Metallic sodium was used as the negative electrode sheet, a Celgard 2400 microporous polypropylene membrane was used as the separator, and NaPF6 (sodium hexafluorophosphate) / EC (ethylene carbonate)-DMC (dimethyl carbonate) was used as the electrolyte. Sodium-ion batteries were then assembled. Charging tests were performed on the assembled sodium-ion batteries, and the results are as follows: Figure 4 As shown.

[0107] The lithium oxalate prepared in Example 1 has a low decomposition voltage (4.2-4.3V) and a specific capacity of 520 mAh / g, while the lithium oxalate prepared in Comparative Example 1 has a high decomposition voltage (4.3-4.5V) and a specific capacity of 438 mAh / g. The superior performance of Example 1 is attributed to the nanoscale material and the thorough and uniform mixing of lithium oxalate and catalyst, which facilitates the catalyst in reducing the decomposition voltage of lithium oxalate and increasing its capacity.

[0108] The sodium oxalate prepared in Example 7 had a low decomposition voltage (4.2-4.3V) and a specific capacity of 400 mAh / g, while the sodium oxalate prepared in Comparative Example 2 had a high decomposition voltage (4.4-4.7V) and a specific capacity of 249 mAh / g. The superior performance of Example 2 is attributed to the nanoscale material and the thorough and uniform mixing of sodium oxalate and catalyst, which facilitates the catalyst in reducing the decomposition voltage of sodium oxalate and increasing its capacity.

[0109] Although the present invention has been illustrated and described with specific embodiments, it should be understood that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; those skilled in the art should understand that modifications can be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein, without departing from the spirit and scope of the present invention; and these modifications or substitutions 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 invention; therefore, this means that all such substitutions and modifications that fall within the scope of the present invention are included in the appended claims.

Claims

1. An additive for supplementing lithium or sodium, characterized in that, It is mainly made of oxalic acid, salt and catalyst; the preparation method includes the following steps: after mixing the mixture containing oxalic acid, salt, catalyst and water, it is subjected to sand milling and spray drying; The salt includes lithium salt or sodium salt; the lithium salt includes Li2CO3 and / or LiOH; the sodium salt includes at least one of NaOH, Na2CO3 or NaHCO3. The particle size distribution concentration of the lithium or sodium supplementation additive satisfies the following formula: 1≤(D90-D10) / D50≤100; The specific surface area of ​​the lithium or sodium supplement is S, and S satisfies the following formula with respect to the D10, D50, and D90 of the lithium or sodium supplement: 1≤S / ((D90-D10) / D50)≤100.

2. The lithium or sodium supplement additive according to claim 1, characterized in that, The D50 values ​​of the oxalic acid, the salt, the catalyst, and the lithium or sodium supplementation additive are Da, Db, Dc, and Dd, respectively, and Da, Db, Dc, and Dd satisfy the following 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 particle size of the lithium or sodium supplement is 0.01~50μm.

5. The lithium or sodium supplement additive according to claim 1, characterized in that, The pH of the lithium or sodium supplement is <7.

6. The lithium or sodium supplement additive according to claim 1, characterized in that, The loose packing density of the lithium or sodium supplement is 0.5~1.5 g / cm³. 3 .

7. The lithium or sodium supplement additive according to claim 1, characterized in that, The catalyst includes: LiCoO2, LiNi x Co y Mn 1-x-y O2, LiFePO4, LiMn x Fe 1-x O4, LiMn2O4, LiNi 0.5 Mn 1.5 O4, 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; in the LiNi x Co y Mn 1-x-y O2, x + y = 1, 0 < x ≤ 1, 0 < y < 1; in the LiMn x Fe 1-x O4, 0 ≤ x ≤ 1.

8. The lithium or sodium supplement additive according to claim 1, characterized in that, The grinding time is 15-30 minutes.

9. The lithium or sodium supplement additive according to claim 1, characterized in that, The material filling efficiency of the mill is 40%~80%.

10. The lithium or sodium supplement additive according to claim 1, characterized in that, The spray drying pressure is 0.2~1.0 MPa.

11. A positive electrode material, characterized in that, The additives include those for lithium or sodium supplementation as described in any one of claims 1 to 10.

12. A lithium-ion or sodium-ion battery, characterized in that, Includes the cathode material as described in claim 11.

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