CN114899391A - Ultra-high nickel single crystal anode material and preparation method thereof - Google Patents
Ultra-high nickel single crystal anode material and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 239000013078 crystal Substances 0.000 title claims abstract description 63
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 62
- 239000010405 anode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 150000001768 cations Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 8
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 27
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 238000005245 sintering Methods 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 20
- 239000007774 positive electrode material Substances 0.000 claims description 19
- 239000010406 cathode material Substances 0.000 claims description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims description 17
- -1 lithium salt compound Chemical class 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 3
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052744 lithium Inorganic materials 0.000 abstract description 20
- 238000001354 calcination Methods 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000007599 discharging Methods 0.000 abstract description 7
- 239000013589 supplement Substances 0.000 abstract description 6
- 238000003837 high-temperature calcination Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 4
- 230000008020 evaporation Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 239000011572 manganese Substances 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 238000005056 compaction Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910018626 Al(OH) Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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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- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- C30B1/00—Single-crystal growth directly from the solid state
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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Abstract
The invention discloses an ultra-high nickel single crystal anode material and a preparation method thereof, and LiNi is synthesized by adopting a solid phase method echelon calcination combined with echelon lithium supplement technology x Co y M 1‑x‑y O 2 (ii) a The adoption of echelon calcination has shorter calcination time compared with a single high-temperature platform, can realize nucleation and rapid growth of single crystal particles under the relatively short high-temperature calcination platform to form a frame of the ultra-high nickel single crystal material, simultaneously avoids the phenomenon of poor lithium caused by lithium evaporation due to overlong high-temperature calcination time, and solves the problem of poor lithium of the ultra-high nickel single crystal anode material Li + /Ni 2+ Serious cation mixing and discharging,The problems of increase of lattice oxygen defects, volatilization of lattice lithium and the like; the surface structure of the material can be effectively repaired by stepwise lithium supplement, and Li caused by high-temperature synthesis is inhibited + /Ni 2+ The cation is mixed and discharged, so that the surface residual alkali is effectively reduced, and the discharge capacity and the cycling stability of the material are improved; the process is completely compatible with the existing production line equipment, and cost reduction iteration of the ultra-high nickel single crystal product can be effectively realized.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an ultra-high nickel single crystal cathode material and a preparation method thereof.
Background
With the wide application of lithium ion batteries in the fields of electric vehicles, energy storage and the like, the demand of the anode materials, particularly lithium cobaltate, lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate ternary anode materials, is also increased dramatically. However, due to the scarcity of cobalt resources, "high nickel and low cobalt" becomes an important concern and development direction in the lithium ion battery industry in recent years.
The high nickel anode material (Ni molar content is more than 80%) obtains wide attention and research and development by virtue of the advantages of high capacity, low cost and the like, and the industrialization pace is gradually accelerated. However, when the Ni content in the layered high-nickel positive electrode material is increased, structural instability is caused by dissimilarity lattice contraction in a deep charge state, local stress concentration is generated along grain boundaries, and microcracks develop, so that the electrolyte infiltrates and erodes the interior of secondary grains, resulting in severe side reactions.
The research finds that the single crystal cathode material has many advantages which are not possessed by the secondary spherical particles, including: the mechanical strength is high, the compaction density is high, and crushing is not easy; secondly, intergranular cracking caused by anisotropic expansion rarely exists; the surface is smooth and can be fully contacted with the conductive agent; fourthly, the surface area is smaller.
The preparation of the prior ultra-high nickel single crystal anode material needs to adopt higher calcination temperature, increase the content of lithium salt or add fluxing agent, and a multi-step calcination process to promote the growth of single crystal particles, so that Ni is caused under the condition of high temperature 3+ The decomposition causes the increase of residual alkali on the surface, finally leads to the gelation of the anode slurry and causes coating difficulty; meanwhile, the poor lithium phenomenon occurs in lithium evaporation caused by high-temperature calcination, so that the electrode material Li + /Ni 2+ The cation is mixed and discharged, and finally the reversible specific capacity of the electrode material is sharply reduced; in addition, a washing process is required to remove lithium salts or flux which are not completely reacted, however, the ultra-high nickel material is sensitive to water, resulting in recombination of a surface structure and capacity loss during the washing process.
Therefore, to suppress Li + /Ni 2+ The cation mixed arrangement and the decomposition of lithium nickelate need to use lower temperature (about 700 ℃) to produce the ultra-high nickel single crystal anode material, and the lower temperature is not beneficial to single crystal nucleation, so that the performance of the ultra-high nickel anode material is poor.
Therefore, most of the single crystal positive electrode materials reported so far have a nickel content of less than 90%, and their preparation requires a reduction in lithiation temperature, making it difficult to synthesize single crystal materials by high temperature.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the ultrahigh nickel single crystal cathode material and the preparation method thereof, the frame structure of the ultrahigh nickel single crystal material is quickly formed at high temperature, and the repair of the surface structure of the material is finished by secondary low-temperature lithium supplement to inhibit Li caused by primary high-temperature synthesis + /Ni 2+ Cation mixed discharging; the initial specific discharge capacity of the ultra-high nickel single crystal anode material is more than 210mAh/g, the capacity retention rate after 50 cycles is more than 92%, and the compaction density is 3.2g/cm 3 ～3.4g/cm 3 It has the advantages of low cost and high specific capacity.
In order to achieve the purpose, the invention adopts the following technical scheme:
an ultra-high nickel single crystal anode material with a chemical formula of LiNi x Co y M 1-x-y O 2 Wherein M is at least one of Al, Ce, Y, Zn, Si, W, B, Cr, Nb, Mg, V, P, La, Sr, Zr, Sn, F, C, Na, Ca, S and Sb, and x is more than or equal to 0.9 and less than 1, 0<y≤0.04，0＜1-x-y≤0.06。
Further, the particle diameter D of the ultra-high nickel single crystal cathode material 50 2 to 6 μm, and a specific surface area of 0.4m 2 /g~0.8 m 2 /g。
Furthermore, the content of LiOH in the ultra-high nickel single crystal anode material is less than or equal to 5500 ppm, and Li 2 CO 3 The content is less than or equal to 3500 ppm, and Li in the structure + /Ni 2+ Ratio of mixed cation discharge<5%。
In order to achieve the purpose, the invention also adopts the following technical scheme:
a preparation method of an ultra-high nickel single crystal cathode material comprises the following steps:
s1, uniformly mixing an ultrahigh nickel hydroxide precursor, a lithium salt compound, an A-element-containing compound, a B-element-containing compound and a C-element-containing compound to obtain a mixture;
s2, sintering the mixture obtained in the step S1 for the first time and then crushing the mixture to obtain crushed materials;
and S3, adding a lithium salt compound into the crushed material obtained in the step S2, uniformly mixing, and then carrying out secondary sintering to obtain the ultra-high nickel single crystal cathode material.
Further, in step S1, the chemical formula of the ultra-high nickel hydroxide precursor is Ni x Co y M 1-x-y (OH) 2 Particle diameter D of the particles 50 2 to 4 μm, and a specific surface area of 6m 2 /g~30 m 2 (ii)/g; element A is one of Y, Mg; b element is one of Al, Ti or W; the C element is one of Zr and Nb.
Further, in the step S1, the mass of the element a in the element a-containing compound is Ni x Co y M 1-x-y O 2 0.05% -0.3% of the mass; the mass of the B element in the B element-containing compound is Ni x Co y M 1-x-y O 2 0.05% -0.3% of the mass; the mass of the C element in the C element-containing compound is Ni x Co y M 1-x-y O 2 0.05-0.3% of the mass, and the total mass of the compound containing the element A, the compound containing the element B and the compound containing the element C is Ni x Co y M 1-x-y O 2 0.15-0.5% of the mass.
Further, the lithium salt compound in each of the step S1 and the step S2 is selected from any one of lithium hydroxide monohydrate, lithium carbonate, lithium nitrate, lithium oxide, lithium acetate, and lithium oxalate, and in the step S1, the molar ratio of the metal element in the ultra-high nickel hydroxide precursor to the lithium element in the lithium salt compound is 1: (0.9-1.1).
Further, in step S2, the specific process of primary sintering is as follows: firstly, heating to 450-550 ℃ at a heating rate of 1-3 ℃/min, preserving heat for 2 hours, heating to 800-900 ℃ at a heating rate of 2-3 ℃/min, preserving heat for 3-6 hours, and then cooling to room temperature at a cooling rate of 2-3 ℃/min.
Further, in the step S3, the mass of the lithium salt compound is 0.5% to 5% of the mass of the crushed material, and the device used for the secondary mixing is selected from any one of a high-speed mixer, a double-cone mixer, a coulter mixer and a planetary ball mill.
Further, in step S3, the secondary sintering specifically includes: firstly, heating to 600-800 ℃ at a heating rate of 3-5 ℃/min, then preserving heat for 6-10 h, and finally cooling to room temperature.
Compared with the prior art, the invention has the beneficial effects that:
1. the solid-phase method echelon calcination technology is combined with the echelon lithium supplement technology to realize the synthesis of LiNi with the chemical formula x Co y M 1-x-y O 2 Ultra-high nickel single crystal positive electrode material; the first discharge specific capacity is more than 210mAh/g, the capacity retention rate after 50 cycles is more than 92 percent, and the compaction density is 3.2g/cm 3 ～3.4g/cm 3 (ii) a The method has the advantages of low roasting cost and easy industrialization;
2. by adopting the echelon calcination technology, the calcination time is shorter compared with that of a single high-temperature platform calcination technology, the nucleation and the rapid growth of single crystal particles can be realized under a relatively short high-temperature (800-900 ℃) calcination platform, the frame structure of the ultra-high nickel single crystal material is formed, meanwhile, the phenomenon of poor lithium caused by lithium evaporation due to overlong high-temperature calcination time is avoided, and the problem of poor lithium caused by the evaporation of lithium of the ultra-high nickel single crystal anode material Li is solved + /Ni 2+ Serious cation mixed discharge, increased lattice oxygen defects, lattice lithium volatilization and the like;
3. the surface structure of the material can be effectively repaired by the echelon lithium supplement technology, and Li caused by one-time high-temperature synthesis is inhibited + /Ni 2+ And the cations are mixed and discharged, so that the residual alkali on the surface is effectively reduced, and the discharge capacity and the cycling stability of the material are improved.
Drawings
FIG. 1 is an SEM image of the ultra-high nickel single crystal cathode material obtained in example 1;
FIG. 2 is an SEM image of an ultra-high nickel hydroxide precursor used in example 1;
fig. 3 is a charge-discharge diagram of the ultra-high nickel single crystal positive electrode material obtained in example 1, comparative example 1 and comparative example 2 after being manufactured into a lithium ion battery;
FIG. 4 is a cycle performance diagram of the ultra-high nickel single crystal positive electrode materials obtained in example 1, comparative example 1 and comparative example 2 after being manufactured into a medium lithium ion battery;
fig. 5 is a fine modification diagram of XRD and Rietveld structure of the ultra-high nickel single crystal positive electrode material obtained in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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 invention provides an ultra-high nickel single crystal anode material with a chemical formula of LiNi x Co y M 1-x-y O 2 Wherein M is at least one of Al, Ce, Y, Zn, Si, W, B, Cr, Nb, Mg, V, P, La, Sr, Zr, Sn, F, C, Na, Ca, S and Sb, and x is more than or equal to 0.9 and less than 1, 0<y≤0.04，0＜1-x-y≤0.06。
Preferably, the particle diameter D of the ultra-high nickel single crystal cathode material 50 2 to 6 μm, and a specific surface area of 0.4m 2 /g~0.8 m 2 /g。
Preferably, the ultra-high nickel single crystal cathode material has the LiOH content less than or equal to 5500 ppm and Li 2 CO 3 The content is less than or equal to 3500 ppm, and Li in the structure + /Ni 2+ Ratio of mixed cation discharge<5%。
The invention also provides a preparation method of the ultra-high nickel single crystal cathode material, which comprises the following steps:
s1, uniformly mixing an ultrahigh nickel hydroxide precursor, a lithium salt compound, an A-element-containing compound, a B-element-containing compound and a C-element-containing compound to obtain a mixture;
s2, sintering the mixture obtained in the step S1 for the first time and then crushing the mixture to obtain crushed materials;
and S3, adding a lithium salt compound into the crushed material obtained in the step S2, uniformly mixing, and then carrying out secondary sintering to obtain the ultra-high nickel single crystal cathode material.
Preferably, in step S1, the chemical formula of the ultra-high nickel hydroxide precursor is Ni x Co y M 1-x-y (OH) 2 Particle diameter D of the particles 50 2 to 4 μm, and a specific surface area of 6m 2 /g~30 m 2 (ii)/g; element A is one of Y, Mg; b element is one of Al, Ti or W; the C element is one of Zr and Nb.
Preferably, in step S1, the mass of the element A in the element A-containing compound is Ni x Co y M 1-x-y O 2 0.05% -0.3% of the mass; the mass of the B element in the B element-containing compound is Ni x Co y M 1-x-y O 2 0.05% -0.3% of the mass; the mass of the C element in the C element-containing compound is Ni x Co y M 1-x-y O 2 0.05-0.3% of the mass, and the total mass of the compound containing the element A, the compound containing the element B and the compound containing the element C is Ni x Co y M 1-x-y O 2 0.15-0.5% of the mass.
Preferably, the lithium salt compound in step S1 and step S2 is selected from any one of lithium hydroxide monohydrate, lithium carbonate, lithium nitrate, lithium oxide, lithium acetate, and lithium oxalate, and in step S1, the molar ratio of the metal element in the ultra-high nickel hydroxide precursor to the lithium element in the lithium salt compound is 1: (0.9-1.1).
Preferably, in step S2, the specific process of the primary sintering is as follows: firstly, heating to 450-550 ℃ at a heating rate of 1-3 ℃/min, preserving heat for 2 hours, heating to 800-900 ℃ at a heating rate of 2-3 ℃/min, preserving heat for 3-6 hours, and then cooling to room temperature at a cooling rate of 2-3 ℃/min.
Preferably, in step S3, the mass of the lithium salt compound is 0.5% to 5% of the mass of the pulverized material, and the secondary mixing equipment is selected from any one of a high mixer, a double-cone mixer, a coulter mixer and a planetary ball mill.
Preferably, in step S3, the secondary sintering specifically comprises: firstly, heating to 600-800 ℃ at a heating rate of 3-5 ℃/min, then preserving heat for 6-10 h, and finally cooling to room temperature.
The invention forms the ultra-high nickel single crystal framework through the rapid high temperature of one-time sintering (800-900 ℃), but the high temperature is accompanied with Li + /Ni 2+ Mixed cation and Ni 3+ So that the lithium is supplemented by secondary low-temperature sintering (600-800 ℃), the secondary roasting time is prolonged, and the solid-phase reaction is continued to ensure that the Ni with the reduced surface 2+ Oxidation to Ni 3+ Thus not only effectively repairing the surface structure, but also reducing Li + /Ni 2+ And (4) cation mixing and discharging.
Example 1:
a preparation method of an ultra-high nickel single crystal cathode material comprises the following steps:
s1, mixing 1000g of Ni 0.96 Co 0.03 Mn 0.01 (OH) 2 （D 50 Is 3.1 μm, and has a specific surface area of 10m 2 /g）、452.1g LiOH·H 2 O、0.836g TiO 2 、1.445g Al（OH) 3 、6.75g ZrO 2 Uniformly mixing the materials by a high-speed mixer, setting the rotating speed to be 850 r/min, and mixing for 20 min to obtain a mixture;
s2, crushing the mixture obtained in the step S1 after primary sintering to obtain crushed materials, wherein the primary sintering comprises the following specific steps: placing the mixture in an oxygen atmosphere furnace, firstly heating to 500 ℃ at a heating rate of 1.5 ℃/min, preserving heat for 2h, then heating to 850 ℃ at a heating rate of 1.5 ℃/min, preserving heat for 4h, and then cooling to room temperature at a cooling rate of 2 ℃/min;
s3, adding 10.9 g of LiOH. H into the crushed material obtained in the step S2 2 And O, uniformly mixing by adopting a high-speed mixer, setting the rotating speed to be 850 r/min, mixing for 10 min, and then performing secondary sintering, wherein the specific process of the secondary sintering is as follows: placing the mixture in an oxygen atmosphere furnace, heating to 750 deg.C at a heating rate of 3 deg.C/min, maintaining for 6 hr, cooling to room temperature, pulverizing, and sieving to obtain superfine powderHigh nickel single crystal positive electrode material.
Example 2:
a preparation method of an ultra-high nickel single crystal cathode material comprises the following steps:
s1, mixing 1000g of Ni 0.94 Co 0.03 Mn 0.03 (OH) 2 （D 50 3.5 μm, a specific surface area of 12m 2 /g）、460.5g LiOH·H 2 O、1.672g TiO 2 、2.89g Al (OH) 3 ，13.5g ZrO 2 Uniformly mixing the materials by a high-speed mixer at a rotating speed of 800 r/min for 25 min to obtain a mixture;
s2, crushing the mixture obtained in the step S1 after primary sintering to obtain crushed materials, wherein the primary sintering comprises the following specific steps: placing the mixture in an oxygen atmosphere furnace, firstly heating to 500 ℃ at the heating rate of 2 ℃/min, preserving heat for 2h, then heating to 870 ℃ at the heating rate of 2 ℃/min, preserving heat for 3h, and then cooling to room temperature at the cooling rate of 3 ℃/min;
s3, adding 21.5g of LiOH. H into the crushed material obtained in the step S2 2 And O, uniformly mixing by adopting a high-speed mixer, setting the rotating speed to be 850 r/min, mixing for 16 min, and then performing secondary sintering, wherein the specific process of the secondary sintering is as follows: and (3) placing the mixture in an oxygen atmosphere furnace, firstly heating to 760 ℃ at the heating rate of 3 ℃/min, preserving the heat for 9 hours, finally cooling to room temperature along with the furnace, crushing and sieving the product to obtain the ultra-high nickel single crystal anode material.
Example 3:
a preparation method of an ultra-high nickel single crystal cathode material comprises the following steps:
s1, mixing 1000g of Ni 0.95 Co 0.02 Mn 0.03 (OH) 2 （D 50 3.3 μm, a specific surface area of 15m 2 /g）、468.5g LiOH·H 2 O、2.508g TiO 2 、4.335gAl(OH) 3 、20.25g ZrO 2 Uniformly mixing the materials by a high-speed mixer, setting the rotating speed to be 1000 r/min, and mixing for 30 min to obtain a mixture;
s2, crushing the mixture obtained in the step S1 after primary sintering to obtain crushed materials, wherein the primary sintering comprises the following specific steps: placing the mixture in an oxygen atmosphere furnace, firstly heating to 600 ℃ at the heating rate of 3 ℃/min, preserving heat for 3h, then heating to 850 ℃ at the heating rate of 2 ℃/min, preserving heat for 6h, and then cooling to room temperature at the cooling rate of 2.5 ℃/min;
s3, adding 21.5g of LiOH. H into the crushed material obtained in the step S2 2 And O, uniformly mixing by adopting a high-speed mixer, setting the rotating speed to be 850 r/min, mixing for 16 min, and then performing secondary sintering, wherein the specific process of the secondary sintering is as follows: and (3) placing the mixture in an oxygen atmosphere furnace, firstly heating to 760 ℃ at the heating rate of 3 ℃/min, preserving the heat for 9 hours, finally cooling to room temperature along with the furnace, crushing and sieving the product to obtain the ultra-high nickel single crystal anode material.
Comparative example 1:
a preparation method of an ultra-high nickel single crystal cathode material comprises the following steps:
s1, mixing 1000g of Ni 0.96 Co 0.03 Mn 0.01 (OH) 2 （D 50 3.1 μm, a specific surface area of 10m 2 /g）、452.1g LiOH·H 2 O、0.836g TiO 2 、1.445g Al（OH) 3 、6.75g ZrO 2 Uniformly mixing the materials by a high-speed mixer, setting the rotating speed to be 850 r/min, and mixing for 20 min to obtain a mixture;
s2, placing the mixture obtained in the step S1 in an oxygen atmosphere furnace, heating to 500 ℃ at a heating rate of 1.5 ℃/min, keeping the temperature for 2h, heating to 850 ℃ at a heating rate of 1.5 ℃/min, keeping the temperature for 12h, cooling to room temperature along with the furnace, crushing a product, and sieving to obtain the ultra-high nickel single crystal anode material.
Comparative example 2:
a preparation method of an ultra-high nickel single crystal cathode material comprises the following steps:
s1, mixing 1000g of Ni 0.94 Co 0.03 Mn 0.03 (OH) 2 （D 50 3.5 μm, a specific surface area of 12m 2 /g）、460.5g LiOH·H 2 O、1.672g TiO 2 、2.89g Al (OH) 3 、13.5g ZrO 2 Uniformly mixing the materials by a high-speed mixer, setting the rotating speed to be 800 r/min, and mixing for 25 min to obtain a mixture;
s2, placing the mixture obtained in the step S1 in an oxygen atmosphere furnace, firstly heating to 500 ℃ at the heating rate of 2 ℃/min, preserving heat for 2h, then heating to 870 ℃ at the heating rate of 2 ℃/min, preserving heat for 12h, finally cooling to room temperature along with the furnace, crushing the product, and sieving to obtain the ultra-high nickel single crystal anode material.
Fig. 1 is an SEM image of the ultra-high nickel single crystal positive electrode material obtained in example 1, and it can be seen from the SEM image that the material particles are not uniform in size, and agglomeration appears, and there is no significant agglomeration.
FIG. 2 is an SEM image of an ultra-high nickel hydroxide precursor used in example 1; ni as seen from the figure 0.96 Co 0.03 Mn 0.01 (OH) 2 The particle size is uniform, the sphericity is good, and no obvious agglomeration exists.
FIG. 5 is a fine modification of the XRD and Rietveld structure of the ultra-high nickel single crystal positive electrode material obtained in example 1, and it can be seen from the figure that the prepared material has a hexagonal layered structure and good crystallinity, I (003) /I (104) >1.2，Li + /Ni 2+ The degree of cation shuffling is low.
The electrochemical performance of the ultra-high nickel single crystal cathode materials obtained in the above examples 1 to 3 and comparative examples 1 to 2 was tested using a button lithium ion battery. The ultra-high nickel single crystal positive electrode materials obtained in the embodiments 1-3 and the comparative examples 1-2 are assembled into a CR2032 button cell, a Land cell test system is adopted to test the first discharge capacity of the button cell under the conditions of 25 ℃ and 0.2C charge and discharge within the voltage range of 2.5V-4.25V, and a constant current charge and discharge mode is used to carry out charge and discharge under the room temperature condition, the voltage range is 2.5-4.25V, and the current density is 60 mA/g (0.3C multiplying power) for 50 circles of charge and discharge circulation. Fig. 3 is a charge-discharge diagram of the ultra-high nickel single crystal positive electrode material obtained in example 1, comparative example 1 and comparative example 2 after being manufactured into a lithium ion battery; fig. 4 is a graph showing cycle performance of the ultra-high nickel single crystal positive electrode materials obtained in example 1, comparative example 1, and comparative example 2 after being fabricated into medium lithium ion batteries.
The collected LiOH content and Li content of the ultra-high nickel single crystal positive electrode materials obtained in examples 1-3 and comparative examples 1-2 2 CO 3 Content, Li + Content, Li in the Material Structure + /Ni 2+ The cation mixing and discharging ratio, the compaction density of the positive electrode sheet (compaction density = area density/(density after rolling the electrode sheet-current collector thickness)), and the first cycle specific charge capacity, first cycle specific discharge capacity, first cycle coulombic efficiency and capacity retention rate after 50 cycles of the lithium ion battery test are shown in the following table 1.
TABLE 1
As can be seen from table 1:
1. LiOH content and Li content of the ultra-high nickel single crystal positive electrode materials obtained in examples 1 to 3 2 CO 3 Content, residual Li + Content, Li + /Ni 2+ The cation mixing and discharging proportion is obviously lower than that of the comparative examples 1-2.
2. The ultrahigh nickel single crystal ternary material provided by the invention has excellent electrochemical properties: the first-cycle charging specific capacity is more than 242mAh/g, the first-cycle discharging specific capacity is more than 210mAh/g, the first-cycle coulombic efficiency is more than 86%, the capacity retention rate after 50-cycle circulation is more than 91%, and the performances are superior to those of comparative example 1 and comparative example 2.
The invention reduces the reaction time of high-temperature calcination and increases a secondary low-temperature calcination platform by adopting the echelon calcination technology, so that the material has lower surface residual lithium compound and low Li + /Ni 2+ The cation mixing and discharging proportion; meanwhile, the secondary lithium supplement technology is adopted, so that the surface structure of the material is reconstructed, and the capacity of the material is recovered.
The points to be finally explained are: although the present invention has been described in detail with reference to the general description and the specific embodiments, on the basis of the present invention, the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and 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.
Claims (10)
1. An ultra-high nickel single crystal anode material is characterized in that the chemical formula of the material is LiNi x Co y M 1-x-y O 2 Wherein M is at least one of Al, Ce, Y, Zn, Si, W, B, Cr, Nb, Mg, V, P, La, Sr, Zr, Sn, F, C, Na, Ca, S and Sb, and x is more than or equal to 0.9 and less than 1, 0<y≤0.04，0＜1-x-y≤0.06。
2. The ultra-high nickel single crystal positive electrode material as claimed in claim 1, wherein the particle diameter D of the ultra-high nickel single crystal positive electrode material 50 2 to 6 μm, and a specific surface area of 0.4m 2 /g~0.8 m 2 /g。
3. The ultra-high nickel single crystal positive electrode material as claimed in claim 1, wherein the ultra-high nickel single crystal positive electrode material has a LiOH content of 5500 ppm or less and Li 2 CO 3 The content is less than or equal to 3500 ppm, and Li in the structure + /Ni 2+ Ratio of mixed cation discharge<5%。
4. The method for preparing the ultra-high nickel single crystal positive electrode material as claimed in any one of claims 1 to 3, comprising the steps of:
s1, uniformly mixing an ultrahigh nickel hydroxide precursor, a lithium salt compound, an A-element-containing compound, a B-element-containing compound and a C-element-containing compound to obtain a mixture;
s2, sintering the mixture obtained in the step S1 for the first time and then crushing the mixture to obtain crushed materials;
and S3, adding a lithium salt compound into the crushed material obtained in the step S2, uniformly mixing, and then carrying out secondary sintering to obtain the ultra-high nickel single crystal cathode material.
5. The method of claim 4, wherein in step S1, the chemical formula of the ultra-high nickel hydroxide precursor is Ni x Co y M 1-x-y (OH) 2 Particle diameter D of the particles 50 2 to 4 μm, and a specific surface area of 6m 2 /g~30 m 2 (ii)/g; element A is one of Y, Mg; b element is one of Al, Ti or W; the C element is one of Zr and Nb.
6. The method according to claim 5, wherein in step S1, the mass of the element A in the element A-containing compound is Ni x Co y M 1-x-y O 2 0.05% -0.3% of the mass; the mass of the B element in the B element-containing compound is Ni x Co y M 1-x- y O 2 0.05% -0.3% of the mass; the mass of the C element in the C element-containing compound is Ni x Co y M 1-x-y O 2 0.05-0.3% of the mass, and the total mass of the compound containing the element A, the compound containing the element B and the compound containing the element C is Ni x Co y M 1-x-y O 2 0.15-0.5% of the mass.
7. The method according to claim 5, wherein the lithium salt compound in each of the step S1 and the step S2 is selected from any one of lithium hydroxide monohydrate, lithium carbonate, lithium nitrate, lithium oxide, lithium acetate, and lithium oxalate, and in the step S1, the molar ratio of the metal element in the ultra-high nickel hydroxide precursor to the lithium element in the lithium salt compound is 1: (0.9-1.1).
8. The method according to claim 4, wherein in step S2, the specific process of the first sintering is: firstly, heating to 450-550 ℃ at a heating rate of 1-3 ℃/min, preserving heat for 2 hours, heating to 800-900 ℃ at a heating rate of 2-3 ℃/min, preserving heat for 3-6 hours, and then cooling to room temperature at a cooling rate of 2-3 ℃/min.
9. The method of claim 4, wherein in step S3, the mass of the lithium salt compound is 0.5% to 5% of the mass of the pulverized material, and the secondary mixing is performed using a device selected from any one of a high-speed mixer, a double-cone mixer, a coulter mixer, and a planetary ball mill.
10. The method according to claim 8, wherein in step S3, the secondary sintering comprises: firstly, heating to 600-800 ℃ at a heating rate of 3-5 ℃/min, then preserving heat for 6-10 h, and finally cooling to room temperature.
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