CN114361443B - Single crystal ternary material, preparation method thereof and lithium battery - Google Patents
Single crystal ternary material, preparation method thereof and lithium battery Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 133
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 56
- 239000013078 crystal Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 60
- 238000005245 sintering Methods 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000011812 mixed powder Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 230000001502 supplementing effect Effects 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 12
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 9
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 9
- 239000013589 supplement Substances 0.000 claims description 4
- 238000005056 compaction Methods 0.000 abstract description 19
- 238000009826 distribution Methods 0.000 abstract description 6
- 230000009469 supplementation Effects 0.000 abstract description 6
- 238000005253 cladding Methods 0.000 abstract 1
- 230000003020 moisturizing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 10
- 239000011572 manganese Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000000428 dust Substances 0.000 description 6
- 238000011049 filling Methods 0.000 description 5
- 238000010902 jet-milling Methods 0.000 description 5
- 238000009766 low-temperature sintering Methods 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a monocrystal ternary material, a preparation method thereof and a lithium battery, and belongs to the technical field of battery materials. The preparation method of the material comprises the following steps: crushing a material obtained by mixing a monocrystal ternary material precursor with a molecular formula of Ni 0.6CO0.1Mn0.3(OH)2 and lithium salt after primary sintering to obtain a crushed material, and collecting micro powder generated in the crushing process; mixing the crushed materials and the micro powder after lithium supplementation to obtain mixed powder, and then coating metal oxide on the surface of the mixed powder and carrying out secondary sintering. Through collecting the miropowder, mix with the crushing material after the moisturizing and carry out cladding and secondary sintering, on the one hand can effectively improve the granularity distribution of single crystal ternary material, promote the compaction density of material, on the other hand, can carry out recycle to this part miropowder, reduction in production cost. The monocrystal ternary material prepared by the method has higher compaction density, and the corresponding lithium battery has higher volumetric energy density.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a monocrystal ternary material, a preparation method thereof and a lithium battery.
Background
Unlike the model numbers NCM523, NCM622, NCM811, etc. defined according to the nickel cobalt manganese ratio, single crystal ternary materials are named according to the morphology of the material itself. From the appearance, the single crystal is single dispersed particles, and the corresponding polycrystalline ternary material is secondary particles with primary particles agglomerated.
Compared with the performances of the monocrystal ternary material and the polycrystal ternary material, the monocrystal ternary material system has more excellent safety performance and cycle performance.
With policy changes, the energy density requirement of the lithium battery is higher and higher, the compaction density is an important factor affecting the energy density of the lithium battery, and the compaction density of the existing monocrystal ternary material is about 3.2-3.4g/cm 3, so that the high-performance requirement of the lithium battery needs to be further improved.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a preparation method of a monocrystal ternary material, which can effectively improve the granularity distribution of the monocrystal ternary material and improve the compaction density of the material.
The second object of the present invention is to provide a single crystal ternary material prepared by the above preparation method.
The third object of the present invention is to provide a lithium battery containing the above single crystal ternary material.
The application can be realized as follows:
in a first aspect, the application provides a method for preparing a single crystal ternary material, comprising the steps of:
Crushing a material obtained by mixing a monocrystal ternary material precursor and lithium salt after primary sintering to obtain a crushed material with the granularity of D 50 =3-3.5 mu m, and collecting micro powder with the granularity of D 50 =1-1.5 mu m generated in the crushing process;
Carrying out lithium supplementing treatment on the micro powder, mixing the crushed material and the micro powder subjected to lithium supplementing to obtain mixed powder, and then coating metal oxide on the surface of the mixed powder and carrying out secondary sintering;
the molecular formula of the monocrystal ternary material precursor is Ni 0.6CO0.1Mn0.3(OH)2;
the lithium supplementing treatment is to mix the micro powder and the lithium supplementing agent and sinter the mixture for 4 to 6 hours at a low temperature of between 200 and 300 ℃.
In an alternative embodiment, the ground material is mixed with the micropowder in a weight ratio of 10-20:1.
In an alternative embodiment, the lithium supplement is used in an amount of 1000 to 2000ppm by weight of the micropowder.
In an alternative embodiment, the lithium supplementing agent comprises at least one of lithium acetate and lithium oxide.
In an alternative embodiment, the weight ratio of single crystal ternary material precursor to lithium salt is 1:1.02-1.08, preferably 1:1.05.
In an alternative embodiment, the primary sintering is performed at 900-950 ℃ for 8-12 hours.
In an alternative embodiment, the secondary sintering is performed at 500-600 ℃ for 6-10 hours.
In a second aspect, the present application provides a single crystal ternary material prepared by the method of any one of the preceding embodiments.
In an alternative embodiment, the single crystal ternary material has a compacted density of 3.6 to 3.8g/cm 3.
In a third aspect, the present application provides a lithium battery, the material of which comprises the single crystal ternary material of the foregoing embodiment.
The beneficial effects of the application include:
The application can make the micro powder continuously grow by collecting the micro powder and the lithium supplementing agent in the grinding process and sintering the micro powder and the lithium supplementing agent under the low temperature condition (lithium supplementing treatment), effectively remove the edges and corners of the micro powder monocrystal, make the micro powder become round, repair the surface structure of the micro powder, and simultaneously prevent the micro powder from damaging the surface structure of the grinding material in the mixing process with the grinding material. After lithium supplementing, the powder is mixed with the crushed material and is coated and sintered for the second time, so that on one hand, the granularity distribution of the monocrystal ternary material can be effectively improved, the compaction density of the material is improved, and on the other hand, the part of micro powder can be recycled, and the production cost is reduced.
The monocrystal ternary material prepared by the method has higher compaction density, and the corresponding lithium battery has higher volumetric energy density.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The monocrystalline ternary material, the preparation method thereof and the lithium battery provided by the application are specifically described below.
The application provides a preparation method of a monocrystal ternary material, which comprises the following steps:
Crushing a material obtained by mixing a monocrystal ternary material precursor and lithium salt after primary sintering to obtain a crushed material with the granularity of D 50 =3-3.5 mu m, and collecting micro powder with the granularity of D 50 =1-1.5 mu m generated in the crushing process; the molecular formula of the monocrystal ternary material precursor is Ni 0.6CO0.1Mn0.3(OH)2.
For reference, the lithium salt may include at least one of lithium hydroxide and lithium carbonate, for example.
The weight ratio of the monocrystal ternary material precursor to the lithium salt can be 1:1.02-1.08, such as 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07 or 1:1.08, and the like, and can also be any other value in the range of 1:1.02-1.08.
In some preferred embodiments, the weight ratio of single crystal ternary material precursor to lithium salt is 1:1.05.
In the present application, the primary sintering temperature after mixing the single crystal ternary material precursor with the lithium salt may be 900 ℃, 905 ℃, 910 ℃, 915 ℃, 920 ℃, 925 ℃, 930 ℃, 935 ℃, 940 ℃, 945 ℃, 950 ℃ or the like, or may be any other value within the range of 900 to 950 ℃.
The time of one sintering may be 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h or 12h, etc., or any other value within the range of 8-12 h.
The crushing after sintering can be carried out by adopting a jet crushing mode, and crushing materials with preset granularity are obtained after jet crushing treatment, wherein the granularity of the part of crushing materials is D 50 =3-3.5 μm.
In the prior art, the conventional method is to directly coat and secondarily sinter the crushed material with the preset granularity after the crushing treatment, and the micro powder with smaller particle size (D 50 =1-1.5 μm) generated in the crushing process is directly used as the waste.
The inventors propose by research: the micro powder with the particle size is collected at the dust collection position and is mixed with the crushed material again according to a certain proportion, so that the part of the material can be effectively recycled, the material waste is avoided, the production cost is greatly reduced, more importantly, the part of micro powder can be filled in gaps among the particles of the crushed material, the particle size distribution of the monocrystal ternary material is improved, and the compaction density of the material is improved.
It should be emphasized that the particle size of the fine powder collected in the present application needs to be strictly controlled within the range of D 50 =1-1.5 μm, if D 50 is larger than 1.5 μm, the filling effect cannot be effectively achieved, and even the situation that filling cannot be achieved at all may exist; however, if the D 50 of the micro powder is smaller than 1 μm, side reactions in the reaction process are increased, which is not beneficial to control the reaction process and affects the normal performance of the material.
In the application, the crushed material and the micro powder after lithium supplement are mixed to obtain the mixed powder.
Incidentally, the weight ratio of the pulverized material to the fine powder when mixed may be 10 to 20:1, such as 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1 or 20:1, etc., and may be any other value within the range of 10 to 20:1.
When the weight ratio of the two is less than 10:1, excessive filling, excessive material fine powder, increased specific surface area, deterioration of material circulation, increased internal resistance and the like can be caused. When the weight ratio of the two is more than 20:1, the filling amount is too small, and the effect of effective filling cannot be achieved.
In the application, the lithium supplementing treatment is further included on the micro powder before the micro powder is mixed with the crushed material.
Alternatively, the lithium supplementing treatment may be low-temperature sintering at 200-300 ℃ for 4-6 hours after mixing the micro powder with the lithium supplementing agent.
The lithium supplementing agent may include at least one of lithium acetate and lithium oxide, among others, by way of example and not limitation. Specifically, the lithium supplementing agent may be lithium acetate alone, lithium oxide alone, or a mixture of lithium acetate and lithium oxide.
The lithium supplement may be used in an amount of 1000 to 2000ppm, such as 1000ppm, 1100ppm, 1200ppm, 1300ppm, 1400ppm, 1500ppm, 1600ppm, 1700ppm, 1800ppm, 1900ppm or 2000ppm, by weight of the powder, or any other value in the range of 1000 to 2000 ppm.
The amount of the lithium supplementing agent is lower than 1000ppm, the effect of effectively removing the edges and corners of the micro powder single crystal cannot be achieved, the amount of the lithium supplementing agent is higher than 2000ppm, and the residual alkali on the surface of the material is too high after the mixed coating is subjected to secondary burning, so that slurry jelly is caused by excessively high water absorption of the residual alkali on the surface in the process of manufacturing the battery coating, and meanwhile, the irreversible capacity loss is increased by the residual alkali on the surface, and adverse effects such as cycle deterioration and the like are caused.
The low temperature sintering temperature may be 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, or the like, or may be any other value within the range of 200-300 ℃.
The low-temperature sintering time can be 4h, 4.5h, 5h, 5.5h or 6h, and the like, and can be any other value in the range of 4-6 h.
The micro powder and the lithium supplementing agent are mixed according to the proportion and sintered under the low-temperature condition, so that the micro powder can continuously grow, the edges and corners of the micro powder single crystal are effectively removed, the micro powder surface structure is repaired, and meanwhile, the surface structure of a crushed material is prevented from being damaged in the mixing process of the micro powder and the crushed material. If the low-temperature sintering temperature is lower than 200 ℃, the micro powder cannot realize effective growth, namely the single crystal edges and corners of the micro powder cannot be effectively removed, namely the micro powder cannot be filled in the gaps in a limited way.
Further, coating metal oxide on the surface of the mixed powder and performing secondary sintering.
Reference may be made to the prior art for coated metal oxides such as aluminium oxide, titanium dioxide or magnesium oxide.
The secondary sintering temperature may be 500-600deg.C, such as 500 deg.C, 510 deg.C, 520 deg.C, 530 deg.C, 540 deg.C, 550 deg.C, 560 deg.C, 570 deg.C, 580 deg.C, 590 deg.C or 600 deg.C, etc., or any other value within the range of 500-600deg.C.
The secondary sintering time can be 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h or 10h, etc., and can be any other value within the range of 6-10 h.
On the one hand, the particle size distribution of the monocrystal ternary material can be effectively improved, the compaction density of the material is improved, and on the other hand, the part of micro powder can be recycled, so that the production cost is reduced.
Correspondingly, the application also provides a monocrystal ternary material prepared by the preparation method.
The single crystal ternary material thus produced has a relatively high compacted density, for example, the corresponding single crystal ternary material has a compacted density in the range of 3.6-3.8g/cm 3.
In addition, the application also provides a lithium battery, the manufacturing material (positive electrode material) of which comprises the single crystal ternary material, and the lithium battery has higher volume energy density.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a monocrystal ternary material, and the preparation method thereof is as follows:
the monocrystal ternary material precursor with the molecular formula of Ni 0.6CO0.1Mn0.3(OH)2 and lithium hydroxide are mixed according to the weight ratio of 1:1.05, and then sintered for 10 hours at the temperature of 925 ℃.
And (3) carrying out jet milling on the material after primary sintering to obtain milled material with the granularity of D 50 =3-3.5 mu m, and collecting micro powder with the granularity of D 50 =1-1.5 mu m generated in the milling process at a dust collecting position.
Mixing the micropowder with lithium acetate, and sintering at low temperature of 250deg.C for 5 hr. Wherein the dosage of the lithium acetate is 1500ppm of the weight of the micropowder.
Mixing the crushed materials and the micro powder subjected to lithium supplementation according to the weight ratio of 15:1 to obtain mixed powder, coating aluminum oxide on the surface of the mixed powder, and carrying out secondary sintering for 8 hours at 550 ℃.
Example 2
The embodiment provides a monocrystal ternary material, and the preparation method thereof is as follows:
Mixing a monocrystal ternary material precursor with a molecular formula of Ni 0.6CO0.1Mn0.3(OH)2 and lithium hydroxide according to a weight ratio of 1:1.02, and then sintering for 12 hours at 900 ℃.
And (3) carrying out jet milling on the material after primary sintering to obtain milled material with the granularity of D 50 =3-3.5 mu m, and collecting micro powder with the granularity of D 50 =1-1.5 mu m generated in the milling process at a dust collecting position.
Mixing the micropowder with lithium acetate, and sintering at 200deg.C for 4 hr. Wherein the dosage of the lithium acetate is 1000ppm of the weight of the micropowder.
Mixing the crushed materials and the micro powder subjected to lithium supplementation according to the weight ratio of 10:1 to obtain mixed powder, coating aluminum oxide on the surface of the mixed powder, and carrying out secondary sintering for 10 hours at the temperature of 500 ℃.
Example 3
The embodiment provides a monocrystal ternary material, and the preparation method thereof is as follows:
Mixing a monocrystal ternary material precursor with a molecular formula of Ni 0.6CO0.1Mn0.3(OH)2 with lithium hydroxide according to a weight ratio of 1:1.08, and then sintering for 8 hours at 945 ℃.
And (3) carrying out jet milling on the material after primary sintering to obtain milled material with the granularity of D 50 =3-3.5 mu m, and collecting micro powder with the granularity of D 50 =1-1.5 mu m generated in the milling process at a dust collecting position.
Mixing the micropowder with lithium acetate, and sintering at 300 deg.C for 4 hr. Wherein the amount of lithium acetate is 2000ppm by weight of the micropowder.
Mixing the crushed materials and the micro powder subjected to lithium supplementation according to the weight ratio of 20:1 to obtain mixed powder, coating aluminum oxide on the surface of the mixed powder, and carrying out secondary sintering for 6h at 600 ℃.
Example 4
The embodiment provides a monocrystal ternary material, and the preparation method thereof is as follows:
the monocrystal ternary material precursor with the molecular formula of Ni 0.6CO0.1Mn0.3(OH)2 and lithium hydroxide are mixed according to the weight ratio of 1:1.05, and then sintered for 10 hours at the temperature of 925 ℃.
And (3) carrying out jet milling on the material after primary sintering to obtain milled material with the granularity of D 50 =3-3.5 mu m, and collecting micro powder with the granularity of D 50 =1-1.5 mu m generated in the milling process at a dust collecting position.
Mixing the micropowder with lithium oxide, and sintering at low temperature of 250deg.C for 5 hr. Wherein the amount of lithium oxide is 1500ppm by weight of the micropowder.
Mixing the crushed materials and the micro powder subjected to lithium supplementation according to the weight ratio of 15:1 to obtain mixed powder, coating aluminum oxide on the surface of the mixed powder, and carrying out secondary sintering for 8 hours at 550 ℃.
That is, this embodiment differs from embodiment 1 in that: the lithium supplementing agent is lithium oxide.
Example 5
The embodiment provides a monocrystal ternary material, and the preparation method thereof is as follows:
the monocrystal ternary material precursor with the molecular formula of Ni 0.6CO0.1Mn0.3(OH)2 and lithium carbonate are mixed according to the weight ratio of 1:1.05, and then sintered for 10 hours at 930 ℃.
And (3) carrying out jet milling on the material after primary sintering to obtain milled material with the granularity of D 50 =3-3.5 mu m, and collecting micro powder with the granularity of D 50 =1-1.5 mu m generated in the milling process at a dust collecting position.
Mixing the micropowder with lithium acetate, and sintering at low temperature of 250deg.C for 5 hr. Wherein the amount of lithium oxide is 1500ppm by weight of the micropowder.
Mixing the crushed materials and the micro powder subjected to lithium supplementation according to the weight ratio of 15:1 to obtain mixed powder, coating aluminum oxide on the surface of the mixed powder, and carrying out secondary sintering for 8 hours at 550 ℃.
That is, this embodiment differs from embodiment 1 in that: the lithium salt is lithium carbonate.
Comparative example 1
The difference between this comparative example and example 1 is that: the micropowder particle size D 50 = 0.5-0.8 μm.
Comparative example 2
The difference between this comparative example and example 1 is that: the micropowder particle size D 50 = 2-2.5 μm.
Comparative example 3
The difference between this comparative example and example 1 is that: mixing the crushed materials and the micro powder according to the weight ratio of 5:1.
Comparative example 4
The difference between this comparative example and example 1 is that: mixing the crushed materials and the micro powder according to the weight ratio of 30:1.
Comparative example 5
The difference between this comparative example and example 1 is that: the amount of the lithium supplementing agent is 500ppm of the weight of the micropowder.
Comparative example 6
The difference between this comparative example and example 1 is that: the dosage of the lithium supplementing agent is 2500ppm of the weight of the micropowder.
Comparative example 7
The difference between this comparative example and example 1 is that: the low temperature sintering temperature is 180 ℃.
Comparative example 8
The difference between this comparative example and example 1 is that: the micropowder is directly mixed with the crushed materials without lithium supplementing treatment.
Comparative example 9
The difference between this comparative example and example 1 is that: the micropowder is not collected, and the crushed material is directly coated with metal oxide and sintered for the second time.
Test example 1
The finished materials obtained in the examples and comparative examples were subjected to a compaction density test.
Compaction density testing:
Taking the ternary materials in each example and each comparative example as 14 parts of samples to be tested, respectively mixing each sample to be tested (5 g), a positive electrode conductive agent (carbon black, 0.28 g) and a positive electrode binder (PVDF, 0.28 g) into a die with the diameter of 2cm, and pressing the powder to the highest compressible height h under the pressure of 10Mpa, so as to obtain the compaction density of the powder: p=5/pi r 2 h. The test results are shown in tables 1 and 2.
TABLE 1 results of compaction Density test
TABLE 2 results of compaction Density test
As can be seen from Table 1, the compaction density of the single crystal ternary material prepared by the method provided by the application is in the range of 3.6-3.8g/cm 3. Wherein, the single crystal ternary material prepared in the example 1 has the highest compaction density, which indicates that the process conditions provided in the example are optimal.
As can be seen from Table 2, the single crystal ternary materials prepared by the method provided by the comparative examples all have a compaction density of less than 3.6g/cm 3.
Test example 2
Lithium batteries were fabricated using the single crystal ternary materials prepared in examples 1 to 5 and comparative examples 1 to 9 as positive electrode materials.
The main preparation steps and conditions are as follows:
And (3) testing the buckling performance: the monocrystal ternary material is manufactured into 2025 button cell, and electrochemical performance test is carried out, wherein the preparation and test conditions are as follows:
positive electrode: SP: pvdf=90:5:5 (mass ratio);
And (3) a negative electrode: a metal lithium;
electrolyte solution: new world nation (M10);
the charging and discharging voltage range is 2.8-4.4V (the nominal capacity is 190 mAh/g);
the battery was charged and discharged at 0.1C, and the test results are shown in tables 3 and 4.
TABLE 3 buckling test results
TABLE 4 buckling test results
As can be seen from tables 3 and 4, example 1 has the highest 0.1C gram capacity.
The results of the energy density per unit volume=compacted density×g capacity calculation test are shown in tables 5 and 6 by the formula.
TABLE 5 energy Density test results
TABLE 6 energy Density test results
As can be seen from tables 5 and 6, the examples have a higher capacity density per unit volume than the comparative examples, and the capacity density per unit volume of the preferred example 1 is 725.3mAh.
In summary, according to the application, the micro powder in the crushing process is collected, the lithium is supplemented, and then the mixture is mixed with the crushed material, and the mixture is coated and sintered for the second time, so that on one hand, the particle size distribution of the monocrystal ternary material can be effectively improved, the compaction density of the material is improved, and on the other hand, the part of micro powder can be recycled, and the production cost is reduced. The monocrystal ternary material prepared by the method has higher compaction density, and the corresponding lithium battery has higher volumetric energy density.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the monocrystal ternary material is characterized by comprising the following steps of: crushing a material obtained by mixing a monocrystal ternary material precursor and lithium salt after primary sintering to obtain a crushed material with the granularity of D 50 =3-3.5 mu m, and collecting micro powder with the granularity of D 50 =1-1.5 mu m generated in the crushing process;
Carrying out lithium supplementing treatment on the micro powder, mixing the crushed material and the micro powder subjected to lithium supplementing to obtain mixed powder, and then coating metal oxide on the surface of the mixed powder and carrying out secondary sintering;
The molecular formula of the monocrystal ternary material precursor is Ni 0.6CO0.1Mn0.3(OH)2;
The lithium supplementing treatment is to mix the micro powder with a lithium supplementing agent and then sinter the mixture for 4 to 6 hours at a low temperature of between 200 and 300 ℃;
The crushed materials and the micro powder are mixed according to the weight ratio of 10-20:1; the dosage of the lithium supplementing agent is 1000-2000ppm of the weight of the micro powder.
2. The method of claim 1, wherein the lithium supplement comprises at least one of lithium acetate and lithium oxide.
3. The method of preparation according to claim 1 or 2, wherein the weight ratio of the single crystal ternary material precursor to the lithium salt is 1:1.02-1.08.
4. A method of preparing according to claim 3, wherein the weight ratio of the single crystal ternary material precursor to the lithium salt is 1:1.05.
5. The method according to claim 1, wherein the primary sintering is performed at 900 to 950 ℃ for 8 to 12 hours.
6. The method according to claim 1, wherein the secondary sintering is performed at 500 to 600 ℃ for 6 to 10 hours.
7. A single crystal ternary material prepared by the method of any one of claims 1-6.
8. The single crystal ternary material of claim 7, wherein the single crystal ternary material has a compacted density of 3.6-3.8g/cm 3.
9. A lithium battery, characterized in that the manufacturing material of the lithium battery comprises the single crystal ternary material according to claim 7 or 8.
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