CN113690419A - Ternary positive electrode composite material, preparation method thereof and lithium ion battery - Google Patents
Ternary positive electrode composite material, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion battery anode materials, in particular to a ternary anode composite material, a preparation method thereof and a lithium ion battery. The ternary cathode composite material has a core-shell structure, and the core-shell structure has a chemical general formula of LiaNibCocMndMeO2Is a core of a compound of the formula (II) with the chemical formula LixNi(0.5‑y)Mn(1.5+y)O4The compound of (a) is a shell; wherein a is more than or equal to 1 and less than or equal to 1.2, b is more than or equal to 0.8 and less than or equal to 1, C is more than 0 and less than 0.2, d is more than 0 and less than 0.2, b + C + d is 1, e is more than 0 and less than or equal to 0.01, and M is selected from CAt least one of s, Ru, Ce, Sm, Sr, Ir, V, Zr, W, Nb and Mo; x is more than or equal to 1 and less than or equal to 1.2, and y is more than or equal to 0 and less than or equal to 0.2. The ternary cathode composite material has the advantages of low total alkali content, excellent cyclicity, stability and safety performance and the like.
Description
Technical Field
The invention relates to the technical field of ternary cathode materials, in particular to a ternary cathode composite material, a preparation method thereof and a lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, good cycle performance and the like, and is widely applied to various fields of electronic products, automobiles, spaceflight and the like. With the increasing requirements of people on environmental protection, endurance, service life and the like of lithium ion batteries, the design and optimization of the batteries are more and more important. As a core in lithium ion batteries, the quality of the positive electrode material directly determines the performance of the battery. The ternary cathode material has become an important cathode active material of the current power lithium ion battery, and has been commercialized in a large scale, such as NCM523, NCM622, and the like. Compared with the traditional LiNiO2，LiCoO2And LiMnO2The material, the ternary positive electrode material, has a more stable structure, better cycle performance and higher capacity.
However, the NCM ternary positive electrode material also has defects such as micro-cracks, phase transition, mechanical stress, and side reactions between the electrode and the electrolyte during the similar cycle, which may cause problems of structural damage, irreversible capacity loss, and the like. In addition, the ternary cathode material in the prior art is of a pure-phase layered crystal structure, and the stability of the ternary cathode material is poorer as the content of nickel is increased, so that the safety cannot be guaranteed. Simultaneously, the increase of residual alkali is accompanied, so that the slurry is unstable and is in a jelly shape during subsequent homogenization.
In addition, the traditional synthesis process of the ternary cathode material is to synthesize a precursor through coprecipitation, and then mix lithium and calcine to obtain a target product, and the process has the following defects: more industrial wastewater is generated, more synthetic process steps are required, the cost is higher, the doping is surface doping, and the stabilizing effect is not obvious.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a ternary cathode composite material, which forms a core-shell structure by doping modification and coating a layer of nano spinel nickel-manganese material, and has the advantages of low total alkali content, excellent cyclicity, stability and safety performance and the like.
The second purpose of the invention is to provide a preparation method of the ternary cathode composite material, the method comprises the steps of doping modification, inducing to form a mixed-arrangement layer, coating a layer of nano spinel lithium nickel manganese oxide to form a core-shell structure, and improving the stability and safety of the material while reducing the residual alkali of the material. In addition, the preparation method also has the advantages of simple process, low cost and the like.
The third purpose of the invention is to provide the lithium ion battery, wherein the anode of the lithium ion battery is mainly prepared from the ternary anode composite material, and the lithium ion battery has the advantages of excellent cyclicity, stability and safety performance, low preparation cost and the like.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the ternary cathode composite material has a core-shell structure, and the core-shell structure adopts a chemical general formula of LiaNibCocMndMeO2Is a core of a compound of the formula (II) with the chemical formula LixNi(0.5-y)Mn(1.5+y)O4The compound of (a) is a shell;
wherein a is more than or equal to 1 and less than or equal to 1.2, b is more than or equal to 0.8 and less than or equal to 1, c is more than 0 and less than 0.2, d is more than 0 and less than 0.2, b + c + d is 1, e is more than 0 and less than or equal to 0.01, and M is selected from at least one of Cs, Ru, Ce, Sm, Sr, Ir, V, Zr, W, Nb and Mo; x is more than or equal to 1 and less than or equal to 1.2, and y is more than or equal to 0 and less than or equal to 0.2.
According to the invention, a core-shell structure is formed by doping modification and coating a layer of nano spinel nickel-manganese material, so that the ternary cathode composite material has the advantages of low total alkali content, excellent cyclicity, stability and safety performance and the like.
The invention also provides a preparation method of the ternary cathode composite material, which comprises the following steps:
(a) mixing a nickel source, a cobalt source, a manganese source, a lithium source and a doping agent with water, grinding, drying and calcining to obtain the nuclear material with the core-shell structure;
(b) crushing and sieving the nuclear material obtained in the step (a), testing the total alkali of the nuclear material after sieving, and according to the test result and the chemical general formula Li of the spinel lithium nickel manganese oxidexNi(0.5-y)Mn(1.5+y)O4And x is more than or equal to 1 and less than or equal to 1.2, y is more than or equal to 0 and less than or equal to 0.2, the addition amounts of the nickel source and the manganese source are obtained by calculation, and the nickel source and the manganese source are added, mixed and then calcined to obtain the ternary cathode composite material.
According to the invention, the mixed-arrangement layer is formed by doping modification and induction, and the nano spinel nickel lithium manganate is coated to form a core-shell structure, so that the stability and safety of the material are improved while the residual alkali of the material is reduced. In addition, the preparation method also has the advantages of simple process, low cost and the like.
The preparation method directly carries out bulk phase doping in the raw material, so that the doping elements uniformly enter the interior of crystal lattices. Therefore, the stability of the cathode material is improved more than that of the conventional surface doping.
Wherein the method for testing the total alkali of the core material specifically comprises the following steps:
dispersing a certain amount of anode material in deionized water, stirring and dispersing for a certain time (generally more than 30 minutes), then filtering to obtain supernatant, carrying out acid-base titration with calibrated dilute hydrochloric acid, respectively using phenolphthalein and methyl orange as indicators of titration end points to obtain two titration end points, and calculating to obtain LiOH and Li2CO3The content of (a).
Meanwhile, the coating consumes the residual lithium on the surface of the calcined material, so that a nano spinel lithium nickel manganese oxide coating layer is formed while the residual alkali is reduced, and a core-shell structure is formed.
Preferably, in step (a), the nickel source comprises a salt of nickel and/or an oxide of nickel.
Preferably, the nickel source comprises at least one of nickel oxide, nickel sesquioxide, nickel sulfate, nickel nitrate, and nickel chloride; more preferably nickel oxide.
Preferably, the cobalt source comprises a salt of cobalt and/or an oxide of cobalt.
Preferably, the cobalt source comprises at least one of cobaltosic oxide, cobalt sulfate, cobalt nitrate, and cobalt chloride; more preferably, tricobalt tetroxide.
Preferably, the manganese source comprises a salt of manganese and/or an oxide of manganese.
Preferably, the manganese source comprises at least one of manganous manganic oxide, manganese carbonate, manganese oxide, manganese dioxide, manganese sulfate, manganese nitrate and manganese chloride; more preferably trimanganese tetroxide.
Preferably, the lithium source comprises a salt of manganese and/or a hydroxide of lithium.
Preferably, the lithium source includes at least one of lithium carbonate, lithium hydroxide, lithium nitrate, and lithium sulfate.
The dopant comprises Cs, Rb, Ru, Ce, Sm, Sr, Ir, V, Zr, W, Nb, Mo element salt and/or oxide thereof.
Preferably, the dopant comprises ZrO2、WO3、Nb2O5、MoO3、Cs2O、Rb2O、Ru2O、Ce2O、Sm2O3、SrO、IrO2And V2O5At least one of (1).
Preferably, in step (a), the solids content of the mixed mixture is from 20% to 60%; including but not limited to, a point value of any one of 25%, 30%, 35%, 40%, 45%, 50%, 55%, 58%, or a range value between any two; more preferably 30% to 40%.
Preferably, in step (a), the water is deionized water.
Preferably, in step (a), the milled grinding media comprises zirconia beads having a particle size of 0.1-0.2mm, more preferably, the zirconia beads are 95 zirconium yttrium stabilized zirconia beads.
Preferably, the milling time is 1-5 hours, including but not limited to the point value of any one of 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, or a range of values between any two.
Preferably, in step (a), the grinding is performed in a ceramic grinder.
The ceramic grinding machine achieves the grinding effect by mutual extrusion of the surfaces of the three horizontal rollers and friction at different speeds, and the granularity of the ground material is adjusted by adjusting the size of a gap between the rollers through adjusting the flat-row hand wheel screw, so that the ceramic grinding machine is simple and accurate and is convenient to operate.
Preferably, the D50 of the milled slurry is below 0.4 μm.
Preferably, the drying is spray drying.
More preferably, the particle size of the powder obtained after the spray drying is 5 μm or less.
Preferably, in step (a), the temperature of the calcination is 700-; more preferably 800-.
Preferably, the calcination time is 6 to 20 hours, including but not limited to, the point value of any one of 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 17.5 hours, 18 hours, 18.5 hours, 19 hours, 19.5 hours or a range value between any two, more preferably 8 to 15 hours.
Preferably, in step (a) and/or step (b), the calcination is carried out in an oxygen-containing atmosphere; more preferably, the oxygen-containing atmosphere comprises air and oxygen.
Preferably, in step (b), the manganese source and/or the nickel source has a particle size of 10 to 200 nm.
Preferably, in step (b), the temperature of the calcination is 700-950 ℃, including but not limited to the values of any one of 725 ℃, 750 ℃, 770 ℃, 800 ℃, 820 ℃, 850 ℃, 880 ℃, 900 ℃, 920 ℃, 940 ℃ or the range values between any two, more preferably 800-900 ℃.
Preferably, the calcination time is 4-10 h; including but not limited to, any one or a range of values between 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, more preferably 5-7 h.
The invention also provides a lithium ion battery which comprises the ternary cathode composite material or the ternary cathode composite material prepared by the preparation method of the ternary cathode composite material.
The lithium ion battery has the advantages of good stability, high safety, simple synthesis process, low cost and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) the ternary cathode composite material provided by the invention forms a core-shell structure by doping modification and coating a layer of nano spinel nickel-manganese material, so that the ternary cathode composite material has the advantages of low total alkali content, excellent cyclicity, stability and safety performance and the like.
(2) According to the preparation method of the ternary cathode composite material, the mixed-arrangement layer is formed through doping modification and induction, and the nano spinel lithium nickel manganese oxide is coated to form a core-shell structure, so that the residual alkali of the material is reduced, and the stability and the safety of the material are improved. In addition, the preparation method also has the advantages of simple process, low cost and the like.
(3) The lithium ion battery provided by the invention has the advantages of excellent cyclicity, stability and safety performance, low preparation cost and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows a ternary positive electrode composite material Li provided in example 2 of the present invention1.06Ni0.9Co0.07Mn0.03Rb0.005O2@Li1.06Ni0.35Mn1.65O4SEM image of (d).
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The preparation method of the ternary cathode composite material comprises the following steps:
(a) and a lithium source Li2CO3NiO as nickel source and Co as cobalt source3O4Mn as a source of manganese3O4Dopant Cs2Mixing O and deionized water uniformly (the molar ratio of lithium element, nickel element, cobalt element, manganese element and zirconium element is 1.06: 0.8: 0.1: 0.1: 0.006), forming a suspension with the solid content of 30%, adding the suspension into a ceramic grinding machine, adding 1.6Kg of 95 zirconium yttrium stable zirconium beads with the diameter of 0.2mm, grinding for 2h at the rotating speed of 2000r/min to obtain a slurry with the D50 of 0.31 μm, and spray-drying the slurry at 180 ℃ to obtain the powder with the D50 of 4.2 μm. And calcining the powder in an oxygen atmosphere at 920 ℃ for 12h to obtain the core material with the core-shell structure.
(b) Cooling, crushing and sieving the nuclear material obtained in the step (a), and then testing the total alkali, wherein the result shows that the content of LiOH is 0.42 percent, and Li2CO3The content is 1.23 percent, and the mass of the required coating agent is calculated according to the chemical general formula of the spinel lithium nickel manganese oxide. The obtained core material, nano NiO and nano Mn3O4According to the mass ratio of 100: 1.3: 5.3 burdening, mixing in a high-speed mixer, calcining the mixture in an oxygen atmosphere at 850 ℃ for 5h to obtain the ternary cathode composite material Li with the core-shell structure1.06Ni0.8Co0.1Mn0.1Cs0.006O2@Li1.05Ni0.4Mn1.6O4。
The total alkali of the ternary cathode composite material is tested, and the result shows that the content of LiOH is 0.11 percent, and Li2CO3The content is 0.08%.
Example 2
(a) And a lithium source Li2CO3NiO as nickel source and Co as cobalt source3O4Mn as a source of manganese3O4Dopant Rb2Mixing O and deionized water uniformly (the molar ratio of lithium element, nickel element, cobalt element, manganese element and rubidium element is 1.08: 0.9: 0.07: 0.03: 0.005), forming a suspension with the solid content of 35%, adding the suspension into a ceramic grinding machine, adding 1.6Kg of 95 zirconium yttrium stable zirconium beads with the diameter of 0.15mm, grinding for 3h at the rotating speed of 2500r/min to obtain a slurry with the D50 of 0.25 mu m, and carrying out spray drying on the slurry at the temperature of 180 ℃ to obtain powder with the D50 of 3.1 mu m. And calcining the powder in an oxygen atmosphere at 880 ℃ for 10h to obtain the core material with the core-shell structure.
(b) Cooling, crushing and sieving the nuclear material obtained in the step (a), and then testing the total alkali, wherein the result shows that the content of LiOH is 0.53 percent, and Li is2CO3The content is 1.43 percent, and the mass of the required coating agent is calculated according to the chemical general formula of the spinel lithium nickel manganese oxide. The obtained core material, nano NiO and nano Mn3O4According to the mass ratio of 100: 1.5: 6.3 mixing materials, mixing the materials in a high-speed mixer, calcining the mixed materials in an oxygen atmosphere at 900 ℃ for 7 hours to obtain the ternary cathode composite material Li with the core-shell structure1.06Ni0.9Co0.07Mn0.03Rb0.005O2@Li1.06Ni0.35Mn1.65O4。
The total alkali of the ternary cathode composite material is tested, and the result shows that the content of LiOH is 0.15 percent, and Li2CO3The content is 0.06%.
The ternary cathode composite material prepared in this example was subjected to SEM test, and the results are shown in fig. 1.
As can be seen from figure 1, the ternary cathode material synthesized by the preparation method provided by the invention is a single crystal material, has round particles, good dispersion effect and less fine powder, and ensures that the ternary cathode material has better cycle performance and safety performance when being prepared into a lithium ion battery.
Example 3
(a) The lithium source LiOH and the nickel source Ni are mixed2O3Cobalt source Co3O4Manganese source MnCO3And a dopant Sm2O3Uniformly mixing the mixture with deionized water (the molar ratio of lithium element, nickel element, cobalt element, manganese element and samarium element is 1.1: 0.95: 0.03: 0.02: 0.008), forming a suspension, adding the suspension into a ceramic grinding machine, adding 1.6Kg of 95 zirconium yttrium stable zirconium beads with the diameter of 0.1mm, grinding for 4 hours at the rotating speed of 2500r/min to obtain a slurry with the D50 of 0.15 mu m, and carrying out spray drying on the slurry at the temperature of 180 ℃ to obtain a powder with the D50 of 2.4 mu m. And calcining the powder in an oxygen atmosphere at 800 ℃ for 8h to obtain the core material with the core-shell structure.
(b) Cooling, crushing and sieving the nuclear material obtained in the step (a), and then testing the total alkali, wherein the result shows that the content of LiOH is 0.59 percent, and Li is2CO3The content is 1.64 percent, and the mass of the required coating agent is calculated according to the chemical general formula of the spinel lithium nickel manganese oxide. The obtained core material, nano NiO and nano Mn3O4According to the mass ratio of 100: 2.2: 6.7 mixing materials, mixing the materials in a high-speed mixer, calcining the mixed materials in an oxygen atmosphere at 900 ℃ for 7 hours to obtain the ternary cathode composite material Li with the core-shell structure1.1Ni0.95Co0.03Mn0.02Rb0.008O2@Li1.08Ni0.5Mn1.5O4。
The total alkali of the ternary cathode composite material is tested, and the result shows that the content of LiOH is 0.04 percent, and Li2CO3The content is 0.12%.
Example 4
(a) And a lithium source Li2CO3NiO as nickel source and Co as cobalt source3O4MnO of manganese source2Doping of the siliconAgent IrO2Uniformly mixing the mixture with deionized water (the molar ratio of lithium element, nickel element, cobalt element, manganese element and iridium element is 1.15: 0.85: 0.1: 0.05: 0.01), forming a suspension, adding the suspension into a ceramic grinding machine, adding 1.6Kg of 95 zirconium yttrium stable zirconium beads with the diameter of 0.15mm, grinding for 5 hours at the rotating speed of 2500r/min to obtain a slurry with the D50 of 0.28 mu m, and carrying out spray drying on the slurry at the temperature of 180 ℃ to obtain powder with the D50 of 3.4 mu m. And calcining the powder in an air atmosphere at the temperature of 950 ℃ for 15h to obtain the core material with the core-shell structure.
(b) Cooling, crushing and sieving the nuclear material obtained in the step (a), and then testing the total alkali, wherein the result shows that the content of LiOH is 0.64 percent, and Li is2CO3The content is 1.58 percent, and the mass of the required coating agent is calculated according to the chemical general formula of the spinel lithium nickel manganese oxide. The obtained core material, nano NiO and nano Mn3O4According to the mass ratio of 100: 1.2: 7.1 mixing the raw materials, mixing the raw materials in a high-speed mixer, calcining the mixed materials in an air atmosphere at 950 ℃ for 10h to obtain the ternary cathode composite material Li with the core-shell structure1.15Ni0.85Co0.1Mn0.05Rb0.01O2@Li1.15Ni0.3Mn1.7O4. The total alkali of the ternary cathode composite material is tested, and the result shows that the content of LiOH is 0.08 percent, and Li2CO3The content is 0.09%.
Comparative example 1
This comparative example was prepared essentially identically to example 2, except that: in the step (b), nano NiO and nano Mn are added3O4Substitution to Al2O3According to the nuclear material and Al2O3The mass ratio of (A) to (B) is 100: 0.05, batching; meanwhile, the calcination temperature is modified to 650 ℃, and the calcination time is modified to 5 hours, so that the Al-coated cathode material is obtained. The Al-coated positive electrode material is tested to be full alkali, and the result shows that the content of LiOH is 1.12 percent, and Li2CO3The content is 0.42%.
The results of the total alkali tests of comparative examples 1 to 4 and 1 show that the core-shell structure ternary cathode materials prepared in examples 1 to 4 consume residual alkali remaining in the core material after the first sintering by coating a layer of nano spinel lithium nickel manganese oxide, so that the total alkali of the materials is obviously reduced. Meanwhile, it can be seen by comparing example 2 with comparative example 1 that the conventional Al coating cannot significantly reduce the total alkali.
Test example 1
The ternary positive electrode composite materials prepared in examples 1 to 4 and comparative example 1 and the Al-coated positive electrode material prepared in the comparative example were mixed with carbon black (SP) and polyvinylidene fluoride (PVDF) at a ratio of 92: 4: 4 into N-methyl pyrrolidone (NMP), uniformly mixing, coating on an aluminum foil, drying at 100 ℃ for 4h, cutting into positive plates with the diameter of 12mm, assembling into a button half-cell, standing for 12h, and carrying out electrochemical test, wherein the test results are shown in the following table 1.
TABLE 1 results of electrochemical testing of each group
| Group of | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| 50 weeks circulation (%) | 97.6 | 98.5 | 97.9 | 98.2 | 93.1 |
| DSC(℃) | 231.2 | 235.4 | 229.1 | 230.2 | 215.2 |
As can be seen from table 1, the cycle and safety performance of the batteries manufactured by using the ternary cathode composite materials having the core-shell structure in examples 1 to 4 of the present invention are significantly higher than those of the battery manufactured by using the Al-coated cathode material in comparative example 1. Therefore, the mixed-arrangement layer is formed through doping modification in an inducing mode, the nano spinel nickel lithium manganate is coated to form a core-shell structure, and the stability and safety of the material are remarkably improved while the residual alkali of the material is reduced.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.
Claims (10)
1. The ternary cathode composite material is characterized by having a core-shell structure, wherein the core-shell structure has a chemical general formula of LiaNibCocMndMeO2With the compound of (1) as a nucleus, in the chemical generalIs represented by the formula LixNi(0.5-y)Mn(1.5+y)O4The compound of (a) is a shell;
wherein a is more than or equal to 1 and less than or equal to 1.2, b is more than or equal to 0.8 and less than or equal to 1, c is more than 0 and less than 0.2, d is more than 0 and less than 0.2, b + c + d is 1, e is more than 0 and less than or equal to 0.01, and M is selected from at least one of Cs, Ru, Ce, Sm, Sr, Ir, V, Zr, W, Nb and Mo; x is more than or equal to 1 and less than or equal to 1.2, and y is more than or equal to 0 and less than or equal to 0.2.
2. The method of preparing a ternary positive electrode composite material according to claim 1, comprising the steps of:
(a) mixing a nickel source, a cobalt source, a manganese source, a lithium source and a doping agent with water, grinding, drying and calcining to obtain the nuclear material with the core-shell structure;
(b) crushing and sieving the core material obtained in the step (a), testing the total alkali of the core material after sieving, and according to the test result and the chemical general formula LixNi(0.5-y)Mn(1.5+y)O4And x is more than or equal to 1 and less than or equal to 1.2, y is more than or equal to 0 and less than or equal to 0.2, the addition amounts of the nickel source and the manganese source are calculated, and the nickel source and the manganese source are added, mixed and then calcined to obtain the ternary cathode composite material.
3. The method for preparing a ternary positive electrode composite according to claim 2, wherein, in the step (a), the nickel source comprises a salt of nickel and/or an oxide of nickel; preferably, the nickel source comprises at least one of nickel oxide, nickel sesquioxide, nickel sulfate, nickel nitrate, and nickel chloride; more preferably nickel oxide;
and/or;
the cobalt source comprises a salt of cobalt and/or an oxide of cobalt; preferably, the cobalt source comprises at least one of cobaltosic oxide, cobalt sulfate, cobalt nitrate, and cobalt chloride; more preferably cobaltosic oxide;
and/or;
the manganese source comprises a salt of manganese and/or an oxide of manganese; preferably, the manganese source comprises at least one of manganous manganic oxide, manganese carbonate, manganese oxide, manganese dioxide, manganese sulfate, manganese nitrate and manganese chloride; more preferably trimanganese tetroxide;
and/or;
the lithium source comprises a salt of manganese and/or a hydroxide of lithium; preferably, the lithium source includes at least one of lithium carbonate, lithium hydroxide, lithium nitrate, and lithium sulfate;
and/or;
the dopant comprises Cs, Rb, Ru, Ce, Sm, Sr, Ir, V, Zr, W, Nb, Mo element salt and/or oxide thereof; preferably, the dopant comprises ZrO2、WO3、Nb2O5、MoO3、Cs2O、Rb2O、Ru2O、Ce2O、Sm2O3、SrO、IrO2And V2O5At least one of (1).
4. The method for preparing a ternary positive electrode composite material according to claim 2, wherein in the step (a), the solid content of the mixed mixture is 20% to 60%; preferably 30 to 40 percent.
5. The method of preparing a ternary positive electrode composite according to claim 2, wherein, in step (a), the ground grinding media comprise zirconia beads having a particle size of 0.1-0.2 mm;
preferably, the grinding time is 1-5 h;
preferably, the milled slurry has a D50 of less than 0.4 μm;
preferably, the drying is spray drying; more preferably, the particle size of the powder obtained after the spray drying is 5 μm or less.
6. The method for preparing the ternary cathode composite material as claimed in claim 2, wherein in the step (a), the calcination temperature is 700-1100 ℃; preferably 800 ℃ and 950 ℃;
preferably, the calcination time is from 6 to 20 hours, more preferably from 8 to 15 hours.
7. The method for producing a ternary positive electrode composite according to claim 2, wherein in step (a) and/or step (b), the calcination is performed in an oxygen-containing atmosphere; preferably, the oxygen-containing atmosphere comprises air and oxygen.
8. The method of preparing a ternary positive electrode composite according to claim 2, wherein, in the step (b), the particle size of the manganese source and/or the nickel source is 10 to 200 nm.
9. The method for preparing the ternary cathode composite material as claimed in claim 2, wherein in the step (b), the calcination temperature is 700-950 ℃, more preferably 800-900 ℃;
preferably, the calcination time is 4-10 h; more preferably 5-7 h.
10. A lithium ion battery comprising the ternary positive electrode composite material according to claim 1, or the ternary positive electrode composite material prepared by the method for preparing the ternary positive electrode composite material according to any one of claims 2 to 8.
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