CN115057487A - Single-crystal cobalt-free cathode material, preparation method thereof and lithium ion battery - Google Patents
Single-crystal cobalt-free cathode material, preparation method thereof and lithium ion battery Download PDFInfo
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- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention discloses a single crystal cobalt-free anode material, a preparation method thereof and a lithium ion battery, wherein the method comprises the following steps: carrying out acid treatment on the polycrystalline cobalt-free positive electrode material by adopting an acid solution; and mixing the cobalt-free anode material subjected to acid treatment with lithium salt, and sintering to obtain the single crystal cobalt-free anode material. According to the method, the polycrystalline cobalt-free anode material is etched by using acid, lithium is prepared and sintered to obtain the single crystal cobalt-free anode material, the anode material with dispersed primary particles can be obtained, and the rate capability and the cycle performance are improved. Can be used as a recovery strategy of polycrystalline cathode materials.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries and cobalt-free anode materials, and relates to a single-crystal cobalt-free anode material, a preparation method thereof and a lithium ion battery.
Background
In recent years, the development of the power battery market enters a motorway, the demand of the lithium ion secondary battery is increased explosively as the most reasonable energy storage medium at present, the demand of the positive electrode material is increased along with the continuous improvement of the productivity, the price of the three metals including nickel, cobalt and manganese is increased rapidly as the most mainstream elements of the current positive electrode material, and particularly, the price of the cobalt element is increased by nearly two times from 1 month in 2018 to 1 month in 2022. The price of the battery is also gradually increased, so that the development of the cobalt-free cathode material shows a strong application prospect.
It is noted that lithium nickel manganese oxide (NM) and lithium nickel manganese cobalt (NCM) cathodes having the same Ni content exhibited comparable discharge capacities at 0.1C, while NM cathodes exhibited better cycling and thermal stability relative to NCM, and therefore, development of NM cathodes was expected to replace NCM cathodes. As is well known, compared with polycrystal, single crystal has better safety and cycle performance, and meanwhile, the polycrystalline anode material has 'grain seeds' with good crystal structure, so that the polycrystalline anode material converted into the single crystal anode material has good development prospect.
CN112391671A discloses a method for reconstructing ternary single crystal materials from waste ternary polycrystalline materials, which comprises the following steps: mixing the waste ternary polycrystalline material with an organic mixed solvent to prepare slurry, and removing part of the solvent after ultrasonic treatment to obtain waste ternary polycrystalline material slurry; placing the waste ternary polycrystalline material slurry into a drum mixer for mixing, atomizing and spraying the lithium manganate seed crystal slurry to the drum mixer to obtain a material to be repaired; and carrying out multi-section roasting on the material to be repaired in an air atmosphere to obtain the ternary single crystal material. The reconstruction method has the advantages of simple process, short flow and high economic added value, can realize high-value conversion of the waste ternary material, and the obtained single crystal material has good electrical properties.
CN114196829A discloses a method for recovering nickel-cobalt-manganese cathode material of retired lithium ion battery, which comprises: (1) crushing a nickel-cobalt-manganese positive electrode material in a decommissioned lithium ion battery to obtain a seed crystal, wherein the particle size D50 of the seed crystal is less than 500 nm; (2) uniformly mixing a mixed solution containing a nickel source, a cobalt source and a manganese source with the seed crystal, and adding a precipitator and a complexing agent to carry out coprecipitation reaction to obtain a single crystal nickel-cobalt-manganese material precursor; (3) and uniformly mixing the precursor of the single crystal nickel-cobalt-manganese material with a lithium source and then calcining to obtain the single crystal anode material. The method can convert the nickel-cobalt-manganese polycrystalline material in the retired lithium ion battery into the nickel-cobalt-manganese single crystal material with excellent electrochemical performance, and can better meet the requirement of high-performance battery development.
However, the preparation process of the invention is complicated, the obtained single-particle single crystal has low particle strength, and metal segregation is easily caused in the process of generating a precursor through a precipitation reaction, so that the electrochemical performance is influenced.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is directed to a single crystal cobalt-free cathode material, a method for preparing the same, and a lithium ion battery. The invention adopts direct grain boundary separation to synthesize the single crystal anode material, can keep the properties (such as nickel-manganese gradient concentration) of the original anode material, has no metal segregation process, and keeps the electrochemical performance of the original anode. The single crystal cobalt-free anode material prepared by the method can improve the rate capability and the cycle performance of the single crystal anode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a single crystal cobalt-free cathode material, comprising the steps of:
carrying out acid treatment on the polycrystalline cobalt-free anode material by adopting an acid solution;
and mixing the cobalt-free anode material subjected to acid treatment with lithium salt, and sintering to obtain the single crystal cobalt-free anode material.
According to the method, the polycrystalline cobalt-free anode material is etched by using acid, lithium is prepared and sintered to obtain the single crystal cobalt-free anode material, the anode material with dispersed primary particles can be obtained, and the rate capability and the cycle performance are improved.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
Preferably, the acid in the acid solution comprises at least one of an organic acid, sulfuric acid, hydrochloric acid and nitric acid, preferably an organic acid. Compared with sulfuric acid, hydrochloric acid and nitric acid, impurity elements such as S, Cl and N are not introduced due to decomposition, and the later-stage electrical performance of the anode is not affected by the etching by using organic acid containing C, H, O, so that the organic acid is preferably used for etching.
Preferably, the organic acid includes at least one of formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, adipic acid, oxalic acid, malonic acid, succinic acid, maleic acid, tartaric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, caproic acid, capric acid, stearic acid, and palmitic acid.
Preferably, the concentration of the acid solution is 1mol/L to 2mol/L, such as 1mol/L, 1.2mol/L, 1.3mol/L, 1.5mol/L, 1.7mol/L, 1.8mol/L, 2mol/L, or the like.
Preferably, the acid treatment process is: and adding the polycrystalline cobalt-free cathode material into an acid solution, and stirring.
Preferably, the amount of the polycrystalline cobalt-free cathode material added during the acid treatment is 0.02g/mL to 0.1g/mL, such as 0.02g/mL, 0.03g/mL, 0.05g/mL, 0.07g/mL, 0.08g/mL, or 0.1g/mL, and the like. Wherein the meaning is exemplified by 0.02g/mL, which means that the amount of the polycrystalline cobalt-free cathode material added is 0.02g per 1mL of the acid solution.
Preferably, the temperature of the stirring during the acid treatment is 25 ℃ to 60 ℃, such as 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃ and the like; the stirring time is 8-20 h, such as 8h, 9h, 10h, 12h, 13h, 14h, 15h, 16h, 18h or 20 h.
Preferably, the acid treatment is followed by the steps of separating, washing and drying. Optionally, a sieving step is performed after drying.
The present invention is not particularly limited with respect to the manner of separation, including but not limited to filtration and centrifugation.
In an alternative embodiment, the washing comprises: the separated powder was washed three times or more with deionized water and then three times with ethanol.
The drying method is not limited in the present invention, and may be natural air drying or oven drying, for example, the washed sample may be put into an oven and dried at 80 ℃ for 12 hours.
In a preferred embodiment of the method of the present invention, the particle size D50 of the cobalt-free cathode material after acid treatment is 0.8 μm to 1.5 μm, for example, 0.8 μm, 1 μm, 1.2 μm, 1.3 μm, 1.4 μm, or 1.5 μm; a breaking strength of 30MPa to 45MPa, for example, 30MPa, 32MPa, 35MPa, 38MPa, 40MPa, 42MPa, 43MPa or 45 MPa; the particle size D50 of the acid-treated cobalt-free positive electrode material is expressed by a, the breaking strength of the acid-treated cobalt-free positive electrode material is expressed by b, and a × b is 25MPa × μm to 60MPa × μm, such as 25MPa × μm, 28MPa × μm, 30MPa × μm, 32MPa × μm, 34MPa × μm, 36MPa × μm, 38MPa × μm, 40MPa × μm, 42.5MPa × μm, 45MPa × μm, 47MPa × μm, 48MPa × μm, 50MPa × μm, 52MPa × μm, 55MPa × μm, 57MPa × μm, or 60MPa × μm.
Preferably, the indentation hardness of the cobalt-free cathode material after acid treatment is 4GPa to 15GPa, such as 4GPa, 6GPa, 8GPa, 10GPa, 12GPa, 13GPa or 15 GPa; the Young's modulus is 60GPa to 150GPa, for example 60GPa, 65GPa, 70GPa, 75GPa, 80GPa, 85GPa, 90GPa, 95GPa, 100GPa, 105GPa, 110GPa, 115GPa, 120GPa, 130GPa, 135GPa, 140GPa or 150 GPa; the ratio of Young's modulus to indentation hardness is 10 to 15, for example, 10, 11, 12, 13, 14, or 15.
If the particle size D50 of the cobalt-free cathode material after acid treatment is too small, the subsequent sintering process may still be polycrystalline, and a high-performance cobalt-free single crystal cathode material cannot be obtained.
By designing indentation hardness, Young modulus and breaking strength of the cobalt-free anode material subjected to acid treatment, namely reasonably designing the parameters of the primary cobalt-free particles, the mechanical property of the cobalt-free single crystal anode material can be effectively improved, and the development of a battery with high compaction and high volume energy density is facilitated.
Preferably, in the XRD spectrum of the cobalt-free cathode material after acid treatment, the ratio of the (003) characteristic diffraction peak intensity to the (101) characteristic diffraction peak intensity is 2.0-2.5, such as 2.0, 2.1, 2.2, 2.3, 2.4 or 2.5; (003) the ratio of the characteristic diffraction peak intensity to the characteristic diffraction peak intensity of (104) is 1.5-1.8, such as 1.5, 1.6, 1.7 or 1.8. By designing the reasonable crystal structure orientation, the method is beneficial to improving the cycling stability and reducing the Li/Ni mixed discharge.
In another preferred embodiment of the method of the present invention, the amount of the lithium salt added is 5% to 10%, for example, 5%, 5.5%, 6%, 6.5%, 7%, 8%, 9%, or 10% of the mass of the cobalt-free cathode material after the acid treatment.
Preferably, the sintering temperature is 900 ℃ to 1100 ℃, such as 950 ℃, 955 ℃, 960 ℃, 965 ℃, 970 ℃, 975 ℃, 980 ℃, 985 ℃, 990 ℃, 995 ℃, 1000 ℃, 1005 ℃ or the like.
Preferably, the sintering time is 8h to 20h, such as 8h, 9h, 10h, 12h, 13h, 14h, 15h, 16h, 18h or 20h, etc.
As a preferable technical scheme of the method, the raw material for mixing the cobalt-free cathode material after acid treatment also comprises a coating agent, and the coating agent comprises ZrO 2 、Al 2 O 3 、Ta 2 O 5 、MoO 3 、SiO 2 、Y 2 O 5 、MgO、TiO 2 、WO 3 、Nb 2 O 5 、SrCO 3 And La 2 O 5 At least one of (1).
Preferably, the coating agent is used in an amount of 1000ppm to 3000ppm, for example, 1000ppm, 1200ppm, 1300ppm, 1500ppm, 1700ppm, 1800ppm, 2000ppm, 2200ppm, 2300ppm, 2500ppm, 2750ppm, 2800ppm, 3000ppm, or the like, based on the mass of the single crystal cobalt-free cathode material.
The source of the polycrystalline cobalt-free cathode material is not limited, and the polycrystalline cobalt-free cathode material can be recovered from waste lithium batteries or prepared from raw materials.
Compared with the traditional recovery method, the method of the invention directly converts the polycrystalline anode material into the single crystal anode material, has simple process, excellent performance of the synthesized anode material and excellent rate performance, is favorable for developing the quick-charging battery,
preferably, the preparation method of the polycrystalline cobalt-free cathode material comprises the following steps: mixing lithium salt, cobalt-free precursor and optional dopant, and reacting at high temperature. The mixing method is not particularly limited, and for example, a hand-held mixer may be used to mix the components uniformly.
Preferably, in the preparation method of the polycrystalline cobalt-free cathode material, the cobalt-free precursor is Ni 0.65+a Mn 0.45-a (OH) 2 Wherein 0.00. ltoreq. a.ltoreq.0.25, for example 0, 0.01, 0.02, 0.03, 0.05, 0.07, 0.08, 0.1, 0.12, 0.13, 0.15, 0.17, 0.18, 0.20, 0.22, 0.23 or 0.25, etc.
Preferably, in the preparation method of the polycrystalline cobalt-free cathode material, the particle size D50 of the cobalt-free precursor is 2.5-3.5 μm, such as 2.5 μm, 2.7 μm, 2.8 μm, 2.9 μm, 3.0 μm, 3.1 μm, 3.2 μm, 3.3 μm, 3.4 μm or 3.5 μm; a breaking strength of 10 to 15MPa, for example, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa or 15 MPa; the particle size D50 of the cobalt-free precursor is expressed by c to the power of one half, the breaking strength of the cobalt-free precursor is expressed by D, and the c x D is 14-30 MPa x mum. By the above definition, the strength of the particles can be ensured.
Preferably, in the preparation method of the polycrystalline cobalt-free cathode material, the indentation hardness of the cobalt-free precursor is 2 GPa-3 GPa, such as 2GPa, 2.2GPa, 2.3GPa, 2.4GPa, 2.5GPa, 2.6GPa, 2.8GPa or 3 GPa; young's modulus of 30GPa to 60GPa, for example 30GPa, 32GPa, 34GPa, 35GPa, 38GPa, 40GPa, 42.5GPa, 45GPa, 47GPa, 50GPa, 53GPa, 55GPa, 58GPa or 60 GPa; the ratio of Young's modulus to indentation hardness is 15 to 30, for example 15, 16, 18, 20, 23, 25, 27, 28 or 30.
By designing indentation hardness, Young modulus and breaking strength of the cobalt-free precursor, the mechanical property of the cobalt-free single crystal anode material can be effectively improved, and the development of a battery with high compaction and high volume energy density is facilitated.
Preferably, in the preparation method of the polycrystalline cobalt-free cathode material, the dopant comprises ZrO 2 、Al 2 O 3 、Ta 2 O 5 、MoO 3 、SiO 2 、Y2O 5 、MgO、TiO 2 、WO 3 、Nb 2 O 5 And SrCO 3 At least one of (a).
Preferably, the dopant is used in an amount of 500ppm to 5000ppm, for example, 500ppm, 800ppm, 1000ppm, 1100ppm, 1200ppm, 1500ppm, 1750ppm, 2000ppm, 2200ppm, 2400ppm, 2500ppm, 2600ppm, 2800ppm, 3000ppm, 3300ppm, 3500ppm, 3600ppm, 3800ppm, 4000ppm, 4500ppm, or 5000ppm based on the mass of the single crystal cobalt-free cathode material.
Preferably, in the preparation method of the polycrystalline cobalt-free cathode material, the temperature of the high-temperature reaction is 700 ℃ to 900 ℃, such as 700 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 770 ℃, 780 ℃, 800 ℃, 825 ℃, 850 ℃, 880 ℃, 900 ℃ or the like; the high-temperature reaction time is 8-12 h, such as 8h, 9h, 10h or 12 h.
Preferably, in the preparation method of the polycrystalline cobalt-free cathode material, the temperature rise speed of the high-temperature reaction is 2 ℃/min to 6 ℃/min, such as 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min or 6 ℃/min, and the like; the cooling speed is 4 ℃/min to 6 ℃/min, such as 4 ℃/min, 5 ℃/min or 6 ℃/min; the ratio of the cooling rate to the heating rate is 2-3, such as 2, 2.2, 2.4, 2.5, 2.6, 2.8 or 3.
In an alternative embodiment, the cooling is followed by the steps of ultracentrifugal grinding and sieving.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
the first step is as follows: preparing a cobalt-free positive electrode material, uniformly mixing lithium salt, a cobalt-free precursor and a doping agent by using a handheld mixer, wherein the granularity D50 of the cobalt-free precursor is 2.5-3.5 microns, the breaking strength F is 10-15 MPa, the product of the breaking strength and the half power of the granularity D50 of the cobalt-free precursor is 14-30 MPa, the indentation hardness (H) of the cobalt-free precursor is 2 GPa-3 GPa, the Young modulus (E) is 30 GPa-60 GPa, the ratio (W) of the Young modulus to the indentation hardness is 15-30, reacting at the high temperature of 700-900 ℃ for 8-12H, cooling, performing ultracentrifugal grinding, and sieving;
the second step is that: adding the prepared cobalt-free anode material into 1-2 mol/L oxalic acid solution, stirring for 8-20H at 25-60 ℃, filtering, collecting powder, washing with deionized water for more than three times, then washing with ethanol for three times, putting into an oven for drying, sieving the dried anode material to obtain cobalt-free anode powder, wherein the granularity D50 of the prepared cobalt-free anode material is 0.8-1.5 mu m, the breaking strength F is 30-45 MPa, the product of the breaking strength and the half power of the granularity D50 of the cobalt-free anode material is 25-60 MPa mu m, the indentation hardness (H) is 4-15 GPa, the Young modulus (E) is 60-150 GPa, the ratio of the Young modulus to the indentation hardness (W) is 10-15, and the ratio of the characteristic diffraction peak strength of (003) to the characteristic diffraction peak strength of (101) in XRD is 2.0-2.5, (003) the ratio of the characteristic diffraction peak intensity to the (104) characteristic diffraction peak intensity is 1.5-1.8;
and thirdly, uniformly mixing the cobalt-free anode material powder prepared in the second step with lithium salt and a coating agent, keeping the temperature at 900-1100 ℃ for 8-20H, and sieving to obtain a sintered cobalt-free anode material, wherein the granularity D50 of the cobalt-free anode material is 2.5-3.5 μm, the breaking strength F is 80-100 MPa, the product of the breaking strength and the half power of the granularity D50 of the cobalt-free anode material is 100-200 MPa μm, the indentation hardness (H) is 8-15 GPa, the Young modulus (E) is 150-180 GPa, the ratio (W) of the Young modulus to the indentation hardness is 10-23, the ratio of the (003) characteristic diffraction peak intensity to the (101) characteristic diffraction peak intensity in XRD is 2.0-2.5, and the ratio of the (003) characteristic diffraction peak intensity to the (104) characteristic diffraction peak intensity is 1.5-1.8.
The kind of lithium salt is not particularly limited in the present invention, and includes, but is not limited to, Li 2 CO 3 At least one of LiOH and lithium nitrate.
In a second aspect, the invention provides a single crystal cobalt-free cathode material prepared by the method of the first aspect.
Preferably, the single crystal cobalt-free cathode material has a metal oxide coverage of 60% to 80%, such as 60%, 62%, 65%, 67%, 68%, 70%, 72%, 73%, 75%, 77%, 78%, or 80% or the like, on the surface.
Preferably, the single crystal cobalt-free cathode material has a particle size D50 of 2.5 to 3.5 μm, such as 2.5, 2.7, 2.8, 3.0, 3.2, 3.4, or 3.5 μm, etc.; a breaking strength of 80MPa to 100MPa, for example 80MPa, 82.5MPa, 85MPa, 88MPa, 90MPa, 93MPa, 96MPa, 98MPa or 100 MPa; the particle size D50 of the single crystal cobalt-free positive electrode material is represented as e by the power of one half, the breaking strength of the single crystal cobalt-free positive electrode material is represented as f, and the e x f is 100-200 MPa x mum.
Preferably, the indentation hardness of the single crystal cobalt-free cathode material is 8GPa to 15GPa, such as 8GPa, 9GPa, 10GPa, 11GPa, 12GPa, 13GPa, 14GPa or 15GPa, etc.; young's modulus of 150GPa to 180GPa, for example 150GPa, 155GPa, 160GPa, 165GPa, 170GPa, 175GPa or 180 GPa; the ratio of Young's modulus to indentation hardness is 10 to 23, for example, 10, 12, 14, 15, 17, 18, 20, 21, 22, 23, or the like.
Preferably, in an XRD pattern of the single crystal cobalt-free cathode material, the ratio of the (003) characteristic diffraction peak intensity to the (101) characteristic diffraction peak intensity is 2.0-2.5, such as 2.0, 2.1, 2.2, 2.3 or 2.5; (003) the ratio of the characteristic diffraction peak intensity to the (104) characteristic diffraction peak intensity is 1.5-1.8, such as 1.5, 1.6, 1.7 or 1.8. By designing the reasonable crystal structure orientation, the method is beneficial to improving the cycling stability and reducing the Li/Ni mixed row.
In a third aspect, the invention provides a lithium ion battery, wherein a positive electrode of the lithium ion battery comprises the single crystal cobalt-free positive electrode material of the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the method, the polycrystalline cobalt-free anode material is etched by using acid, lithium is prepared and sintered to obtain the single crystal cobalt-free anode material, the anode material with dispersed primary particles can be obtained, and the rate capability and the cycle performance are improved. Can be used as a recovery strategy of polycrystalline cathode materials.
Furthermore, the etching is carried out by using organic acid containing C, H, O elements, compared with sulfuric acid, hydrochloric acid and nitric acid, impurity elements such as S, Cl, N and the like cannot be introduced due to decomposition, and the later-stage electric performance of the positive electrode is not influenced.
By designing indentation hardness, Young modulus and breaking strength of the cobalt-free anode material subjected to acid treatment, namely reasonably designing the parameters of the primary cobalt-free particles, the mechanical property of the cobalt-free single crystal anode material can be effectively improved, and the development of a battery with high compaction and high volume energy density is facilitated. By designing the reasonable crystal structure orientation, the method is beneficial to improving the cycling stability and reducing the Li/Ni mixed row.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a preparation method of a single crystal cobalt-free cathode material, which comprises the following steps:
the first step is as follows: a cobalt-free positive electrode material was prepared by mixing 48.94g of Li as a lithium salt 2 CO 3 And 100g of cobalt-free precursor Ni 0.65 Mn 0.35 (OH) 2 And 0.3g TiO 2 Uniformly mixing by using a handheld mixer, wherein the granularity D50 of a cobalt-free precursor is 3.0 mu m, the breaking strength F is 12.2MPa, the product of the breaking strength and the half power of the granularity D50 of the cobalt-free precursor is 21.13MPa mu m, the indentation hardness (H) of the cobalt-free precursor is 2.46GPa, the Young modulus (E) is 43.5GPa, the ratio (W) of the Young modulus and the indentation hardness is 17.7, heating to 800 ℃ at the speed of 2 ℃/min for high-temperature reaction for 10H, cooling to room temperature at the speed of 4 ℃/min, then carrying out ultracentrifugal grinding and sieving;
the second step is that: adding 5g of prepared cobalt-free anode material into 100mL of prepared 1mol/L oxalic acid solution, stirring for 12h at 30 deg.C, filtering, collecting powder, washing with deionized water for more than three times, washing with ethanol for three times, placing into oven, drying at 80 ℃ for 12H, sieving the dried positive electrode material to obtain cobalt-free positive electrode powder, wherein the particle size D50 of the prepared cobalt-free positive electrode material is 1.1 mu m, the breaking strength F is 31.2MPa, the product of the breaking strength and the half power of the particle size D50 of the cobalt-free positive electrode material is 32.72MPa mu m, the indentation hardness (H) is 6.5GPa, the Young modulus (E) is 91.6GPa, the ratio (W) of the Young modulus to the indentation hardness is 14.1, the ratio of the characteristic diffraction peak intensity of (003) to the characteristic diffraction peak intensity of (101) in XRD is 2.1, and the ratio of the characteristic diffraction peak intensity of (003) to the characteristic diffraction peak intensity of (104) is 1.7;
thirdly, 100g of cobalt-free cathode material powder prepared in the second step of repeated preparation and 5g of Li are taken 2 CO 3 And 0.3g of Al 2 O 3 Uniformly mixing, keeping the temperature at 980 ℃ for 10 hours, and sieving to obtain the cobalt-free anode material by sintering to obtain cobalt-free anode Al 2 O 3 The coverage rate is 78.3%, the obtained cobalt-free cathode material granularity D50 is 2.8 μm, the fracture strength F is 91.6MPa, the product of the fracture strength and the half power of the cobalt-free cathode material granularity D50 is 153.3MPa μm, the indentation hardness (H) is 12.5GPa, the Young modulus (E) is 168GPa, the ratio (W) of the Young modulus to the indentation hardness is 13.44, the ratio of the (003) characteristic diffraction peak intensity to the (101) characteristic diffraction peak intensity in XRD is 2.0, and the ratio of the (003) characteristic diffraction peak intensity to the (104) characteristic diffraction peak intensity is 1.5;
example 2
Example 2 differs from example 1 in that the cobalt-free precursor used is Ni 0.75 Mn 0.25 (OH) 2 。
Example 3
Example 3 differs from example 1 in that the lithium salt used in the first step is 48.9g of LiOH.
Example 4
Example 4 differs from example 1 in that the sintering temperature in the first step is 850 ℃.
Example 5
Example 5 differs from example 1 in that the organic acid-soluble solution used in the second step is benzoic acid.
Example 6
Example 6 differs from example 1 in that the sintering temperature used in the third step is 990 ℃.
Comparative example 1
Comparative example 1 differs from example 1 in that the first step uses a precursor with a fracture strength F of 5.2MPa, a fracture strength multiplied by the particle size to the power of one half of 9 MPa/. mu.m, an indentation hardness (H) of 1.5GPa, a Young's modulus (E) of 28.6GPa, and a ratio (W) of the Young's modulus to the indentation hardness of 19, and the precursor is reacted at a high temperature of 800 ℃ for 10H, cooled, ultracentrifugally ground and sieved.
The fracture strength of the precursor of the comparative example is lower than a reasonable range value, and the synthesis process causes structural collapse.
Comparative example 2
Comparative example 2 differs from example 1 in that the first step used a precursor with a breaking strength F of 21.5MPa, a product of the breaking strength and the half power of the cobalt-free precursor particle size D50 of 37.2MPa x μm, an indentation hardness (H) of 5.2GPa, a young's modulus (E) of 60.8GPa, and a ratio of young's modulus to indentation hardness (W) of 11.7, reacted at a high temperature of 800 ℃ for 10H, cooled and then ultracentrifugally ground and sieved.
The rupture strength of the comparative example is higher than a reasonable range value, the synthesis process is not beneficial to the diffusion of Li ions, and the multiple rate of the synthesized anode material is poor.
Comparative example 3
Comparative example 3 differs from example 1 in that the cobalt-free cathode material produced in the second step had a fracture strength F of 15.3MPa, a product of the fracture strength and the power of half of the particle size D50 of 16.0, a product of the fracture strength and the power of half of the particle size of 14.0MPa · μm, an indentation hardness (H) of 3.8GPa, a young's modulus (E) of 58.5GPa, and a young's modulus to indentation hardness ratio (W) of 15.4.
The positive electrode material synthesized by the comparative example is too fine, and the sintering process is still polycrystalline.
Comparative example 4
The difference from example 1 is that the ratio of the intensity of the (003) characteristic diffraction peak to the intensity of the (101) characteristic diffraction peak in XRD of the cobalt-free cathode material produced in the second step is 1.5, and the ratio of the intensity of the (003) characteristic diffraction peak to the intensity of the (104) characteristic diffraction peak is 1.0.
The crystal structure c axis of the cathode material synthesized by the comparative example is too short, which is not beneficial to the later-stage lithium supplement.
Comparative example 5
Comparative example 5 differs from example 1 in that the cobalt-free cathode material produced in the third step had a fracture strength F of 75MPa, a fracture strength multiplied by the particle size to the power of one-half of 125.4MPa × μm, an indentation hardness (H) of 7.8GPa, a young's modulus (E) of 90GPa, and a young's modulus to indentation hardness ratio (W) of 11.5.
The cobalt-free anode material synthesized by the comparative example has low breaking strength and weak bonding force agglomeration.
Comparative example 6
Comparative example 6 is different from example 1 in that the cobalt-free cathode material obtained in the third step had a fracture strength F of 120MPa, a product of the fracture strength and a power of one half of the particle size D50 of 200.8MPa · μm, an indentation hardness (H) of 18.2GPa, a young's modulus (E) of 286.6GPa, and a ratio of the young's modulus to the indentation hardness (W) of 15.74.
The crystal grains of the cobalt-free anode material synthesized by the comparative example are too coarse, and the phenomena of metal partial oxygen loss and the like exist.
Comparative example 7
Comparative example 7 is different from example 1 in that the ratio of the intensity of the (003) characteristic diffraction peak to the intensity of the (101) characteristic diffraction peak in XRD of the cobalt-free cathode material produced in the third step is 3.0, and the ratio of the intensity of the (003) characteristic diffraction peak to the intensity of the (104) characteristic diffraction peak is 3.
The crystal structure c axis of the cathode material synthesized by the comparative example is larger.
Comparative example 8
Comparative example 8 is different from example 1 in that the ratio of the intensity of the (003) characteristic diffraction peak to the intensity of the (101) characteristic diffraction peak in XRD of the cobalt-free cathode material produced in the third step is 2.5, and the ratio of the intensity of the (003) characteristic diffraction peak to the intensity of the (104) characteristic diffraction peak is 1.0.
The crystal structure a axis of the cathode material synthesized by the comparative example is smaller.
Comparative example 9
Comparative example 9 differs from example 1 in that the material taken is a commercially available, normally prepared cobalt-free cathode material.
Comparative example 10
Comparative example 10 is different from example 1 in that the acid solution used in the second step is a 1mol/L sulfuric acid solution.
And (4) buckling and assembling: the method comprises the following steps of taking a metal lithium sheet as a negative electrode, and taking the positive electrode materials prepared in examples 1-6 and comparative examples 1-10 to prepare a positive electrode piece, wherein the positive electrode piece is prepared by taking NMP as a solvent, and the mass ratio of the positive electrode material to a binder (PVDF) to a conductive agent (SP) is 96: 2: 2 evenly mixing and coating on an aluminum foil, wherein the solid content of the PVDF glue solution is 6.05 percent, the thickness of the aluminum foil is 12 mu m, the purity is more than 99 percent, and the pole piece is compacted to be 3.3g/cm 3 The button half cells were assembled with celgard 2325 separator in a vacuum glove box.
Table 1 shows the electrical properties of examples 1 to 6 and comparative examples 1 to 10, (charge cut-off voltage of 4.5V, discharge cut-off voltage of 3.0V, and nominal gram capacity of 200 mAh/g).
TABLE 1
From the above, it is understood that a high-performance single crystal positive electrode material can be obtained by the method of the present invention, and excellent rate capability and cycle performance are exhibited.
Compared with the comparative example 9, the cobalt-free cathode material synthesized by the method disclosed by the invention has the advantages that the rate performance is improved by 2% and the cycle retention rate is improved by 2% compared with the 4C rate performance of the commercially available cobalt-free cathode material, the crystal structure grown by the method for obtaining fine grains is stable, and the lithium ion dynamics is excellent.
Comparing examples 1-6 with comparative example 1, it can be seen that when the fracture strength of the precursor used is lower than the target value, the collapse of the precursor mechanism during the synthesis process causes the synthesized Li/Ni positive electrode material to be unfavorable for the kinetic process of lithium ion transport, and thus the rate performance is poor, and when the fracture strength of the precursor used is higher than the target value, the synthesis process is unfavorable for Li when compared with comparative example 2 + Resulting in poor conductivity of the resultant cathode material, thereby affecting Li + The rate capability becomes worse.
Compared with the comparative example 3, the comparison of the examples 1 to 6 shows that the fracture strength of the grown crystal grains synthesized in the second step is lower than a target value, the grains are too fine and fragile, and the grains are difficult to sinter into single crystal materials in the subsequent sintering process, so that the cycle performance is poor, and large grains with too high fracture strength cannot be generated due to the fact that the grain size of the primary grains of the polycrystalline anode material is too small, so that the method is not analyzed;
comparing examples 1-6 with comparative example 4, it can be seen that the cobalt-free cathode crystal grain synthesized in the second step has a ratio of (003) characteristic diffraction peak intensity to (101) characteristic diffraction peak intensity and a ratio of (003) characteristic diffraction peak intensity to (104) characteristic diffraction peak intensity lower than a target value, and the c axis of the synthesized cathode material is shorter, so that the subsequent lithium supplement process is influenced, and the finally synthesized cathode material has fewer migratable lithium ions, slow kinetics and poor rate capability.
Compared with the comparative example 5, the examples 1-6 show that the finally synthesized cobalt-free positive electrode material has too low fracture strength, which is caused by the fact that a large amount of weak-binding-force aggregates exist in the synthesized positive electrode material, so that the structure is damaged after the pole piece is rolled by a subsequent roller, the cycle performance is poor, and the multiplying power is poor, and compared with the comparative example 6, the synthesized cobalt-free positive electrode material has the defects that the fracture strength is increased, the multiplying power is poor, which is caused by the fact that the grain size of the synthesized cobalt-free positive electrode material is large, the metal segregation process exists, and the performance is poor.
Comparing examples 1-6 with comparative example 7, it can be seen that when the cobalt-free anode synthesized in the third step is synthesized, the ratio of the (003) characteristic diffraction peak intensity to the (101) characteristic diffraction peak intensity in XRD is higher than the target value, and the synthesized anode material c-axis is large, so that the structure collapse is caused in the subsequent battery cycle process, especially under the high-rate charge and discharge, the structure collapse is more serious, and therefore the rate performance is deteriorated, and compared with comparative example 8, it can be seen that the ratio of the (003) characteristic diffraction peak intensity to the (104) characteristic diffraction peak intensity is lower than the target value, so that the a-axis in the synthesized anode material crystal structure is too low, and an irreversible phase transition process exists in the battery cycle process, so that the electrochemical performance is deteriorated.
Comparing examples 1-7 with comparative example 10, it can be seen that the material prepared by using sulfuric acid has poor cycle performance due to the introduction of S impurities caused by the use of sulfuric acid and the shuttle effect of S.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a single crystal cobalt-free cathode material is characterized by comprising the following steps:
carrying out acid treatment on the polycrystalline cobalt-free positive electrode material by adopting an acid solution;
and mixing the cobalt-free anode material subjected to acid treatment with lithium salt, and sintering to obtain the single crystal cobalt-free anode material.
2. The method according to claim 1, wherein the acid in the acid solution comprises at least one of an organic acid, sulfuric acid, hydrochloric acid and nitric acid, preferably an organic acid;
preferably, the organic acid includes at least one of formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, adipic acid, oxalic acid, malonic acid, succinic acid, maleic acid, tartaric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, caproic acid, capric acid, stearic acid, and palmitic acid;
preferably, the concentration of the acid solution is 1 mol/L-2 mol/L;
preferably, the acid treatment process is: adding the polycrystalline cobalt-free cathode material into an acid solution, and stirring;
preferably, in the acid treatment process, the addition amount of the polycrystalline cobalt-free cathode material is 0.02 g/mL-0.1 g/mL;
preferably, in the acid treatment process, the stirring temperature is 25-60 ℃, and the stirring time is 8-20 h;
preferably, the acid treatment is followed by the steps of separating, washing and drying.
3. The method according to claim 1 or 2, characterized in that the particle size D50 of the acid treated cobalt-free positive electrode material is 0.8 μ ι η to 1.5 μ ι η, the breaking strength is 30MPa to 45MPa, the power of one half of the particle size D50 of the acid treated cobalt-free positive electrode material is denoted a, the breaking strength of the acid treated cobalt-free positive electrode material is denoted b, a x b is 25MPa μ ι η to 60MPa μ ι η;
preferably, the indentation hardness of the cobalt-free cathode material after acid treatment is 4 GPa-15 GPa, the Young modulus is 60 GPa-150 GPa, and the ratio of the Young modulus to the indentation hardness is 10-15;
preferably, in the XRD pattern of the cobalt-free cathode material after acid treatment, the ratio of (003) characteristic diffraction peak intensity to (101) characteristic diffraction peak intensity is 2.0-2.5, and the ratio of (003) characteristic diffraction peak intensity to (104) characteristic diffraction peak intensity is 1.5-1.8.
4. The method of any one of claims 1-3, wherein the lithium salt is added in an amount of 5% to 10% by mass of the cobalt-free cathode material after the acid treatment;
preferably, the sintering temperature is 900-1100 ℃;
preferably, the sintering time is 8-20 h.
5. The method according to any one of claims 1 to 4, wherein the raw material for the acid-treated cobalt-free positive electrode material mixture further comprises a coating agent comprising ZrO 2 、Al 2 O 3 、Ta 2 O 5 、MoO 3 、SiO 2 、Y 2 O 5 、MgO、TiO 2 、WO 3 、Nb 2 O 5 、SrCO 3 And La 2 O 5 At least one of;
preferably, the coating agent is used in an amount of 1000ppm to 3000ppm based on the mass of the single crystal cobalt-free cathode material.
6. The method according to any one of claims 1 to 5, wherein the polycrystalline cobalt-free positive electrode material is recovered from spent lithium batteries or is prepared from raw materials.
7. The method of claim 6, wherein the method of preparing the polycrystalline cobalt-free cathode material comprises the steps of: mixing lithium salt, a cobalt-free precursor and an optional dopant, and reacting at a high temperature;
preferably, in the preparation method of the polycrystalline cobalt-free cathode material, the cobalt-free precursor is Ni 0.65+a Mn 0.35-a (OH) 2 Wherein a is more than or equal to 0.00 and less than or equal to 0.25;
preferably, in the preparation method of the polycrystalline cobalt-free cathode material, the particle size D50 of the cobalt-free precursor is 2.5-3.5 μm, the breaking strength is 10-15 MPa, the power of one half of the particle size D50 of the cobalt-free precursor is c, the breaking strength of the cobalt-free precursor is D, and the c × D is 14-30 MPa × μm;
preferably, in the preparation method of the polycrystalline cobalt-free cathode material, the indentation hardness of the cobalt-free precursor is 2 GPa-3 GPa, the Young modulus is 30 GPa-60 GPa, and the ratio of the Young modulus to the indentation hardness is 15-30;
preferably, in the preparation method of the polycrystalline cobalt-free cathode material, the dopant comprises ZrO 2 、Al 2 O 3 、Ta 2 O 5 、MoO 3 、SiO 2 、Y2O 5 、MgO、TiO 2 、WO 3 、Nb 2 O 5 And SrCO 3 At least one of;
preferably, the dosage of the dopant is 500-5000 ppm based on the single crystal cobalt-free cathode material;
preferably, in the preparation method of the polycrystalline cobalt-free cathode material, the temperature of the high-temperature reaction is 700-900 ℃, and the time of the high-temperature reaction is 8-12 h;
preferably, in the preparation method of the polycrystalline cobalt-free cathode material, the temperature rise speed of the high-temperature reaction is 2-6 ℃/min, the temperature reduction speed is 4-6 ℃/min, and the ratio of the temperature reduction speed to the temperature rise speed is 2-3.
8. The method according to any one of claims 1-7, characterized in that the method comprises the steps of:
the first step is as follows: preparing a cobalt-free positive electrode material, uniformly mixing lithium salt, a cobalt-free precursor and a doping agent by using a handheld mixer, wherein the granularity D50 of the cobalt-free precursor is 2.5-3.5 microns, the breaking strength is 10-15 MPa, the product of the breaking strength and the half power of the granularity D50 of the cobalt-free precursor is 14-30 MPa microns, the indentation hardness of the cobalt-free precursor is 2 GPa-3 GPa, the Young modulus is 30 GPa-60 GPa, the ratio of the Young modulus to the indentation hardness is 15-30, reacting at the high temperature of 700-900 ℃ for 8-12 h, cooling, ultra-centrifugal grinding and sieving;
the second step: adding the prepared cobalt-free anode material into 1-2 mol/L oxalic acid solution, stirring for 8-20 h at 25-60 ℃, filtering, collecting powder, washing with deionized water for more than three times, washing the obtained product with ethanol for three times, drying the obtained product in an oven, sieving the dried positive electrode material to obtain cobalt-free positive electrode powder, wherein the granularity D50 of the prepared cobalt-free positive electrode material is 0.8-1.5 microns, the breaking strength is 30-45 MPa, the product of the breaking strength and the half power of the granularity D50 of the cobalt-free positive electrode material is 25-60 MPa, the indentation hardness is 4-15 GPa, the Young modulus is 60-150 GPa, the ratio of the Young modulus to the indentation hardness is 10-15, the ratio of the (003) characteristic diffraction peak strength to the (101) characteristic diffraction peak strength in XRD is 2.0-2.5, and the ratio of the (003) characteristic diffraction peak strength to the (104) characteristic diffraction peak strength is 1.5-1.8;
and thirdly, uniformly mixing the cobalt-free anode material powder prepared in the second step with lithium salt and a coating agent, keeping the temperature at 900-1100 ℃ for 8-20 h, and sieving to obtain a sintered cobalt-free anode material, wherein the granularity D50 of the cobalt-free anode material is 2.5-3.5 μm, the breaking strength is 80-100 MPa, the product of the breaking strength and the half power of the granularity D50 of the cobalt-free anode material is 100-200 MPa μm, the indentation hardness is 8-15 GPa, the Young modulus is 150-180 GPa, the ratio of the Young modulus to the indentation hardness is 10-23, the ratio of the (003) characteristic diffraction peak intensity to the (101) characteristic diffraction peak intensity in XRD is 2.0-2.5, and the ratio of the (003) characteristic diffraction peak intensity to the (104) characteristic diffraction peak intensity is 1.5-1.8.
9. A single crystal cobalt-free cathode material prepared by the method of any one of claims 1 to 8;
preferably, the coverage rate of the metal oxide on the surface of the single crystal cobalt-free cathode material is 60-80%;
preferably, the granularity D50 of the single crystal cobalt-free positive electrode material is 2.5-3.5 μm, the breaking strength is 80-100 MPa, the power of one half of the granularity D50 of the single crystal cobalt-free positive electrode material is recorded as e, the breaking strength of the single crystal cobalt-free positive electrode material is recorded as f, and the e x f is 100-200 MPa-mum;
preferably, the indentation hardness of the single crystal cobalt-free cathode material is 8 GPa-15 GPa, the Young modulus is 150 GPa-180 GPa, and the ratio of the Young modulus to the indentation hardness is 10-23;
preferably, in an XRD pattern of the single crystal cobalt-free cathode material, the ratio of (003) characteristic diffraction peak intensity to (101) characteristic diffraction peak intensity is 2.0-2.5, and the ratio of (003) characteristic diffraction peak intensity to (104) characteristic diffraction peak intensity is 1.5-1.8.
10. A lithium ion battery comprising the single crystal cobalt-free cathode material of claim 9 in a cathode.
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