CN114361441A - Preparation method of in-situ coated single crystal high-nickel ternary cathode material - Google Patents
Preparation method of in-situ coated single crystal high-nickel ternary cathode material Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 54
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000010406 cathode material Substances 0.000 title claims description 27
- 239000000463 material Substances 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- MOOYSSSIVSFZQA-UHFFFAOYSA-N [Li].[Mo] Chemical compound [Li].[Mo] MOOYSSSIVSFZQA-UHFFFAOYSA-N 0.000 claims abstract description 27
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 17
- 239000011733 molybdenum Substances 0.000 claims abstract description 17
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 16
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 claims abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000011812 mixed powder Substances 0.000 claims description 68
- 238000010438 heat treatment Methods 0.000 claims description 43
- 239000007787 solid Substances 0.000 claims description 31
- 238000000227 grinding Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 10
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 10
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical group [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 235000002639 sodium chloride Nutrition 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 230000004907 flux Effects 0.000 claims description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N vanadium(V) oxide Substances O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 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
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229910015667 MoO4 Inorganic materials 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims 1
- 239000013590 bulk material Substances 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 229910001456 vanadium ion Inorganic materials 0.000 claims 1
- 229910013716 LiNi Inorganic materials 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 13
- 239000010405 anode material Substances 0.000 abstract description 10
- 238000009768 microwave sintering Methods 0.000 abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 4
- 239000011247 coating layer Substances 0.000 abstract description 4
- 238000009831 deintercalation Methods 0.000 abstract description 3
- 239000010416 ion conductor Substances 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 16
- 239000012467 final product Substances 0.000 description 12
- 229910001935 vanadium oxide Inorganic materials 0.000 description 8
- 238000005245 sintering Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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- 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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Abstract
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a preparation method of a single crystal high-nickel ternary anode material which is sintered at a low temperature and coated in situ. Mixing Ni0.8Co0.1Mn0.1(OH)2Mixing the raw materials with a lithium source in a certain proportion, simultaneously mixing a molybdenum-containing fluxing agent and a vanadium-containing fluxing agent, calcining the mixture in a microwave sintering furnace at a certain temperature, and preparing the monocrystal LiNi with in-situ coating layer molybdenum lithium vanadate0.8Co0.1Mn0.1O2A material. The surface of the electrolyte is coated with the molybdenum lithium vanadate, so that the electrolyte and the single crystal LiNi can be prevented from being coated with the molybdenum lithium vanadate0.8Co0.1Mn0.1O2Direct contact of the particle surfaces, thereby reducing unwanted side reactions, preventing the growth of CEI films and enhancing single crystal LiNi0.8Co0.1Mn0.1O2And (5) structural stability of the material. And the molybdenum lithium vanadate is a fast ion conductor, so that the lithium ion deintercalation capability can be enhanced, and the multiplying power performance of the material is further improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a preparation method of a single crystal high-nickel ternary anode material which is sintered at a low temperature and coated in situ.
Background
Under the background of continuous temperature rise in the field of new energy automobiles, lithium ion batteries are gradually developed under the promotion of the market. On the level of industrial popularity, the ternary cathode material has excellent performance data. However, with the increasing demand of consumer markets and the continuous development of new energy fields, the performance of the ternary cathode material needs to be further improved to meet the requirement of higher energy density.
Conventional high nickel ternary positive electrode materials are typically spherical secondary particles, agglomerated by nanoscale primary particles. The particles have low mechanical strength and large surface area of primary particles, so that the problems of low mechanical strength, poor high pressure resistance, low compaction density and the like exist, and secondly, the surface of the high-nickel ternary cathode material is unstable and is easy to react with moisture and CO in air2Residual lithium is generated through reaction, and the electrochemical performance of the cathode material is influenced. The single-crystal ternary cathode material well avoids the problems and effectively improves the cycle performance, so that the single-crystal ternary cathode material is very expected to be used as a mainstream cathode material in the market in a power battery system. However, it is not easy to synthesize single crystal cathode materials, particularly nickel-rich ternary cathode materials. So far, the single crystal ternary anode material is generally prepared by adopting a two-stage method high-temperature sintering, namely, the single crystal ternary anode material is prepared by the first-stage high-temperature sintering, and the surface modification is carried out by the second-stage medium-temperature sintering. However, high-temperature sintering easily causes lithium loss, generation of NiO rock salt phase and Li/Ni mixed discharge, and reduces the electrochemical performance of the cathode material. The flux growth method is another synthesis method of the single crystal ternary anode material at present. The addition of the fluxing agent can effectively reduce the sintering temperature of the single crystal ternary material, reduce Li/Ni mixed discharge and improve the electrochemical performance. The conventional fluxing agents at present are mainly KCl, NaCl and LiNO3However, the single-crystal high-nickel ternary cathode material prepared by adopting the fluxing agent also needs to be subsequently washed by water and coated for the second time so as to improve the cathode materialSurface air sensitivity.
In order to solve the technical problem, the scheme provides a novel method for preparing a single crystal high-nickel ternary cathode material with the surface modified in situ by one-step sintering. We used vanadium-containing and molybdenum-containing compounds as fluxing agents. On the one hand, the melting point is lower and the boiling point is higher because the two have stronger fluxing effect. On the other hand, in the process of preparing the single crystal ternary cathode material, the fluxing agent can react with lithium salt to generate a molybdenum lithium vanadate coating layer in situ, so that the effects of improving the electrochemical performance and the structural stability of the material are achieved.
Disclosure of Invention
The invention provides a single crystal LiNi coated with in-situ molybdenum lithium vanadate0.8Co0.1Mn0.1O2A preparation method of the cathode material. Commercial single crystal LiNi0.8Co0.1Mn0.1O2Precursor Ni of material0.8Co0.1Mn0.1(OH)2Mixing the lithium source with a certain proportion, wherein the lithium source is as follows: lithium oxalate, lithium nitrate, lithium carbonate or lithium hydroxide. Simultaneously mixing the molybdenum-containing fluxing agent and the vanadium-containing fluxing agent, calcining the mixture by using a microwave sintering furnace at a certain temperature, and preparing the monocrystal LiNi with the in-situ coating layer molybdenum lithium vanadate0.8Co0.1Mn0.1O2A material. The surface of the electrolyte is coated with the molybdenum lithium vanadate, so that the electrolyte and the single crystal LiNi can be prevented from being coated with the molybdenum lithium vanadate0.8Co0.1Mn0.1O2Direct contact of the particle surfaces, thereby reducing unwanted side reactions, preventing the growth of CEI films and enhancing single crystal LiNi0.8Co0.1Mn0.1O2And (5) structural stability of the material. And the molybdenum lithium vanadate is a fast ion conductor, so that the lithium ion deintercalation capability can be enhanced, and the multiplying power performance of the material is further improved.
The technical effect of the invention is realized by the following technical scheme:
single crystal LiNi coated with molybdenum lithium vanadate in situ0.8Co0.1Mn0.1O2A positive electrode material prepared by a process comprising the steps of:
(1) mixing nickel, cobalt and manganeseHydroxide Ni0.8Co0.1Mn0.1(OH)2Mixing the lithium salt and the lithium salt according to a molar ratio of 1: 1.06-1: 1.2, and fully grinding to obtain mixed powder a;
(2) mixing and uniformly grinding mixed powder b formed by a molybdenum-containing fluxing agent and a vanadium-containing fluxing agent with the mixed powder a to obtain mixed powder c; wherein the mass fraction of the mixed powder b in the mixed powder c is 2-10%;
(3) raising the temperature of the mixed powder c to 120-180 ℃ at a heating rate of 2-10 ℃/min in an oxygen atmosphere, preserving heat for 2-3h, raising the temperature to 400-500 ℃ at a heating rate of 2-10 ℃/min, preserving heat for 4-6 h, raising the temperature to 800-900 ℃ at a heating rate of 1-2 ℃/min, preserving heat for 12-18 h, and cooling with a furnace to obtain a solid block material;
(4) crushing and grinding the solid block material, and mixing the crushed and ground solid block material with deionized water in a ratio of 1: 10, ultrasonically dispersing for 5min, then quickly filtering, placing in a 120 ℃ blast drying oven for drying for 2h, collecting the dried solid, and obtaining the in-situ coated molybdenum lithium vanadate single crystal LiNi0.8Co0.1Mn0.1O2And (3) a positive electrode material.
Preferably, the molar ratio of the nickel-cobalt-manganese hydroxide to the lithium salt in the step (1) is 1: 1.08-1.15.
Preferably, the lithium salt in step (1) is one of lithium hydroxide, lithium carbonate, lithium nitrate and lithium oxalate, and lithium oxalate is preferred.
Preferably, the molar ratio of the metal ion vanadium and the metal ion molybdenum in the vanadium-containing flux and the molybdenum-containing flux in the mixed powder b in the step (2) is 1:1.
Preferably, the vanadium-containing flux in the step (2) is vanadium trioxide (V)2O3) Vanadium pentoxide (V)2O5) Or ammonium metavanadate (NH)4VO3) (ii) a The molybdenum-containing fluxing agent is molybdenum oxide (MoO)3) Or ammonium molybdate ((NH)4)2MoO4)。
Preferably, in the step (2), other fluxing agents may be further added to the mixed powder b, and the other fluxing agents are potassium fluoride (KF) and calcium chloride (CaCl)2) Lithium chloride(LiCl), lead oxide (PbO), boron oxide (B)2O3) And sodium chloride (NaCl).
Preferably, the mass fraction of the other flux is 10% to 50% of the mixed powder b.
Preferably, in the step (3), the mixed powder c is heated to 160 ℃ at a heating rate of 5 ℃/min and is kept for 2h in an oxygen atmosphere, heated to 450 ℃ at a heating rate of 5 ℃/min and is kept for 5h, then heated to 880 ℃ at a heating rate of 1 ℃/min and is kept for 16h, and furnace cooling is carried out to obtain a solid block material.
The invention relates to a lithium ion battery, wherein the anode material of the battery adopts the single crystal NCM ternary material which is coated with molybdenum lithium vanadate in situ.
Has the advantages that:
in the method of the present invention, first, single-crystal LiNi is synthesized0.8Co0.1Mn0.1O2The method comprises the steps of mixing a precursor of a positive electrode material with lithium salt, simultaneously adding a molybdenum-containing fluxing agent and a vanadium-containing fluxing agent, then carrying out heat treatment on the mixed powder, and then carrying out crushing and washing, wherein the molybdenum-containing fluxing agent and the vanadium-containing fluxing agent can promote independent growth of primary particles in the early stage of calcination and control the particle size.
Meanwhile, in the later stage of high-temperature calcination, the molybdenum-containing fluxing agent, the vanadium-containing fluxing agent and lithium salt react to generate the molybdenum lithium vanadate coated on the single crystal LiNi0.8Co0.1Mn0.1O2Finally obtaining micron-sized monocrystal LiNi with good monocrystal appearance and in-situ coated molybdenum lithium vanadate on the surface of the anode material0.8Co0.1Mn0.1O2And (3) a positive electrode material.
In the material prepared by the method, the molybdenum lithium vanadate coating layer can inhibit electrolyte and single crystal LiNi0.8Co0.1Mn0.1O2The direct contact of the anode material reduces the interface side reaction, maintains the stable structure of the material, and simultaneously, the molybdenum lithium vanadate is used as a fast ion conductor, can promote the lithium ion deintercalation and improve the single crystal LiNi0.8Co0.1Mn0.1O2Electrochemical properties of the positive electrode material.
In the method, other fluxing agents are added at the powder mixing stage to further promote the single crystal LiNi0.8Co0.1Mn0.1O2The growth of primary particles of the cathode material and the reduction of the calcination temperature.
In the method, better single crystal LiNi can be obtained by adopting pre-burning treatment in the high-temperature calcination stage0.8Co0.1Mn0.1O2And (3) a positive electrode material.
Drawings
FIG. 1 is a view showing single-crystal LiNi prepared in example 1 and comparative example 10.8Co0.1Mn0.1O2And comparing the cycle performance of the cathode material.
FIG. 2 is a view showing the single-crystal LiNi prepared in example 1 and comparative example 10.8Co0.1Mn0.1O2Graph comparing rate performance of positive electrode material.
FIG. 3 LiNi coated with lithium molybdenum vanadate in example 10.8Co0.1Mn0.1O2SEM image of cathode material
FIG. 4 LiNi coated with lithium molybdenum vanadate in example 10.8Co0.1Mn0.1O2TEM image of positive electrode material
Detailed Description
Comparative example 1:
(1) mixing Ni0.8Co0.1Mn0.1(OH)2Grinding the mixture and lithium oxalate according to a molar ratio of 1:1.08 to obtain mixed powder a;
(2) mixing the mixed powder a, completely mixing with NaCl serving as mixed powder b, and uniformly grinding to obtain powder labeled as mixed powder c, wherein the mass ratio of the mixed powder b in the mixed powder c is controlled to be 4%; the mass fraction of NaCl in the mixed powder b is 100 percent;
(3) then placing the mixed powder c in a microwave sintering furnace, heating to 160 ℃ at a heating rate of 5 ℃/min under an oxygen-introducing state, preserving heat for 2h, heating to 450 ℃ at a heating rate of 5 ℃/min, preserving heat for 5h, heating to 880 ℃ at a heating rate of 1 ℃/min, preserving heat for 16h, and cooling along with the furnace to obtain a solid block material;
(4) crushing and grinding the solid block material, and mixing the crushed and ground solid block material with deionized water in a ratio of 1: 10, ultrasonically dispersing for 5min, then quickly filtering, and then placing in a 120 ℃ air-blast drying oven for 2 h. Collecting the solid and drying to obtain the single crystal LiNi0.8Co0.1Mn0.1O2And (3) a positive electrode material.
According to the scanning electron microscope result of the final product, the final product is single crystal particles, and the surface is smooth and has no impurities.
According to the electrochemical test results of the final product, the assembled battery has a cut-off voltage in the range of 2.8 to 4.3V, 1C (1C ═ 200mAh · g)-1) After the cycle under the multiplying power is cycled for 200 weeks, the capacity retention rate of the final product is found to be 70.8%, and then the multiplying power performance test of 0.1C-5C is carried out, and the discharge capacity reaches 95.2 mAh.g at 5C-1. Which shows that the material has poor cycling stability and rate capability.
Example 1
(1) Mixing Ni0.8Co0.1Mn0.1(OH)2Grinding the mixture and lithium oxalate according to a molar ratio of 1:1.08 to obtain mixed powder a;
(2) weighing mixed powder b of vanadium oxide and molybdenum oxide, mixing the mixed powder b with the mixed powder a, grinding and uniformly mixing to obtain mixed powder c, wherein the mass fraction of the mixed powder b in the mixed powder c is 4%; mixing vanadium oxide and molybdenum oxide in the mixed powder b according to the molar ratio of metal ion vanadium to metal ion molybdenum of 1: 1;
(3) then placing the mixed powder c in a microwave sintering furnace, heating to 160 ℃ at a heating rate of 5 ℃/min under an oxygen-introducing state, preserving heat for 2h, heating to 450 ℃ at a heating rate of 5 ℃/min, preserving heat for 5h, heating to 880 ℃ at a heating rate of 1 ℃/min, preserving heat for 16h, and cooling along with the furnace to obtain a solid block material;
(4) crushing and grinding the solid block material, and mixing the crushed and ground solid block material with deionized water in a ratio of 1: 10, ultrasonically dispersing for 5min, then quickly filtering, and then placing in a 120 ℃ air-blast drying oven for 2 h. Collecting the solid and drying to obtain the single crystal LiNi in which the lithium molybdenum vanadate is coated in situ0.8Co0.1Mn0.1O2A positive electrode material;
according to the scanning electron microscopy result of the prepared material, as shown in FIG. 3, the appearance of the prepared material is micron-sized single crystal particles, and as shown in FIG. 4, the surface of the single crystal particles can be found to have a coating.
According to the electrochemical test results of the final product, the assembled battery has a cut-off voltage in the range of 2.8-4.3V, and after 200 weeks of cycling at 1C rate, the capacity retention rate of the final product is found to be 85.15%. Then, a 0.1C-5C rate capability test is carried out, and the discharge capacity reaches 132.2 mAh.g at 5C-1. The cycle stability and the rate capability of the material coated with the lithium molybdenum vanadate in situ are improved.
Example 2
(1) Mixing Ni0.8Co0.1Mn0.1(OH)2Grinding the mixture and lithium oxalate according to a molar ratio of 1:1.08 to obtain mixed powder a;
(2) weighing mixed powder b of vanadium oxide and molybdenum oxide, mixing the mixed powder b with the mixed powder a, grinding and uniformly mixing to obtain mixed powder c, wherein the mass fraction of the mixed powder b in the mixed powder c is 6%; mixing vanadium oxide and molybdenum oxide in the mixed powder b according to the molar ratio of metal ion vanadium to metal ion molybdenum of 1: 1;
(3) then placing the mixed powder c in a microwave sintering furnace, heating to 160 ℃ at a heating rate of 5 ℃/min under an oxygen-introducing state, preserving heat for 2h, heating to 450 ℃ at a heating rate of 5 ℃/min, preserving heat for 5h, heating to 880 ℃ at a heating rate of 1 ℃/min, preserving heat for 16h, and cooling along with the furnace to obtain a solid block material;
(4) crushing and grinding the solid block material, and mixing the crushed and ground solid block material with deionized water in a ratio of 1: 10, ultrasonically dispersing for 5min, then quickly filtering, and then placing in a 120 ℃ air-blast drying oven for 2 h. Collecting the solid and drying to obtain the single crystal LiNi in which the lithium molybdenum vanadate is coated in situ0.8Co0.1Mn0.1O2A positive electrode material;
according to the scanning electron microscope result of the prepared material, which is similar to that in FIG. 3, the appearance is micron-sized single crystal particles. Similar to fig. 4, it can be seen that the surface of the single crystal particles has a coating.
According to the results of electrochemical tests of the final product, theThe assembled cell was cycled at 1C rate for 200 weeks at a cut-off voltage in the range of 2.8-4.3V, and the final product capacity retention was found to be 83.27%. Then, a 0.1C-5C rate performance test is carried out, and the discharge capacity reaches 127.2 mAh.g at 5C-1. The cycle stability and the rate capability of the material coated with the lithium molybdenum vanadate in situ are improved.
Example 3
(1) Mixing Ni0.8Co0.1Mn0.1(OH)2Grinding the mixture and lithium oxalate according to a molar ratio of 1:1.08 to obtain mixed powder a;
(2) weighing mixed powder b of vanadium oxide and molybdenum oxide, mixing the mixed powder b with the mixed powder a, grinding and uniformly mixing to obtain mixed powder c, wherein the mass fraction of the mixed powder b in the mixed powder c is 8%; mixing vanadium oxide and molybdenum oxide in the mixed powder b according to the molar ratio of metal ion vanadium to metal ion molybdenum of 1: 1;
(3) then placing the mixed powder c in a microwave sintering furnace, heating to 160 ℃ at a heating rate of 5 ℃/min under an oxygen-introducing state, preserving heat for 2h, heating to 450 ℃ at a heating rate of 5 ℃/min, preserving heat for 5h, heating to 880 ℃ at a heating rate of 1 ℃/min, preserving heat for 16h, and cooling along with the furnace to obtain a solid block material;
(4) crushing and grinding the solid block material, and mixing the crushed and ground solid block material with deionized water in a ratio of 1: 10, ultrasonically dispersing for 5min, then quickly filtering, and then placing in a 120 ℃ air-blast drying oven for 2 h. Collecting the solid and drying to obtain the single crystal LiNi in which the lithium molybdenum vanadate is coated in situ0.8Co0.1Mn0.1O2A positive electrode material;
according to the scanning electron microscope result of the prepared material, which is similar to that in FIG. 3, the appearance is micron-sized single crystal particles. Similar to fig. 4, it can be seen that the surface of the single crystal particles has a coating.
According to the electrochemical test results of the final product, the assembled battery has a cut-off voltage in the range of 2.8-4.3V, and after 200 weeks of cycling at 1C rate, the capacity retention rate of the final product is 81.77%. Then, a 0.1C-5C rate capability test is carried out, and the discharge capacity reaches 125.2 mAh.g at 5C-1. Explanation in-situ bagThe cycling stability and the rate capability of the material after the molybdenum lithium vanadate is coated are improved.
Example 4
(1) Mixing Ni0.8Co0.1Mn0.1(OH)2Grinding the mixture and lithium oxalate according to a molar ratio of 1:1.08 to obtain mixed powder a;
(2) weighing mixed powder b of vanadium oxide, molybdenum oxide and lead oxide, mixing the mixed powder b with the mixed powder a, grinding and uniformly mixing to obtain mixed powder c, wherein the mass fraction of the mixed powder b in the mixed powder c is 8%; and mixing vanadium oxide and molybdenum oxide in the mixed powder b according to the metal ion molar ratio of 1:1, mixing, wherein the mass fraction of lead oxide accounts for 40% of the mixed powder b;
(3) then placing the mixed powder c in a microwave sintering furnace, heating to 160 ℃ at a heating rate of 5 ℃/min under an oxygen-introducing state, preserving heat for 2h, heating to 450 ℃ at a heating rate of 5 ℃/min, preserving heat for 5h, heating to 880 ℃ at a heating rate of 1 ℃/min, preserving heat for 16h, and cooling along with the furnace to obtain a solid block material;
(4) crushing and grinding the solid block material, and mixing the crushed and ground solid block material with deionized water in a ratio of 1: 10, ultrasonically dispersing for 5min, then quickly filtering, and then placing in a 120 ℃ air-blast drying oven for 2 h. Collecting the solid and drying to obtain the single crystal LiNi in which the lithium molybdenum vanadate is coated in situ0.8Co0.1Mn0.1O2A positive electrode material;
according to the scanning electron microscope result of the prepared material, which is similar to that in FIG. 3, the appearance is micron-sized single crystal particles. Similar to fig. 4, it can be seen that the surface of the single crystal particles has a coating.
According to the electrochemical test results of the final product, the assembled battery has a cut-off voltage in the range of 2.8-4.3V, and after 200 weeks of cycling at 1C rate, the capacity retention rate of the final product is 82.54%. Then, a 0.1C-5C rate capability test is carried out, and the discharge capacity reaches 122.1 mAh.g at 5C-1. The cycle stability and the rate capability of the prepared single crystal ternary cathode material are improved.
Claims (8)
1. A preparation method of an in-situ coated single crystal high-nickel ternary cathode material is characterized by comprising the following specific steps:
(1) nickel cobalt manganese hydroxide Ni0.8Co0.1Mn0.1(OH)2Mixing the lithium salt and the lithium salt according to a molar ratio of 1: 1.06-1: 1.2, and grinding to obtain mixed powder a;
(2) mixing and uniformly grinding mixed powder b formed by a molybdenum-containing fluxing agent and a vanadium-containing fluxing agent with the mixed powder a to obtain mixed powder c; wherein the mass fraction of the mixed powder b in the mixed powder c is 2-10%;
(3) raising the temperature of the mixed powder c to 120-180 ℃ at a heating rate of 2-10 ℃/min in an oxygen atmosphere, preserving heat for 2-3h, raising the temperature to 400-500 ℃ at a heating rate of 2-10 ℃/min, preserving heat for 4-6 h, raising the temperature to 800-900 ℃ at a heating rate of 1-2 ℃/min, preserving heat for 12-18 h, and cooling with a furnace to obtain a solid block material;
(4) crushing and grinding the solid block material, mixing the crushed and ground solid block material with deionized water, placing the mixture in an air-blast drying oven for drying after ultrasonic dispersion and suction filtration, and collecting the dried solid to obtain the in-situ molybdenum lithium vanadate-coated single crystal LiNi0.8Co0.1Mn0.1O2And (3) a positive electrode material.
2. The method for preparing an in-situ coated single crystal high nickel ternary positive electrode material as claimed in claim 1, wherein in the step (1), the molar ratio of the nickel cobalt manganese hydroxide to the lithium salt is 1: 1.08-1.15; the lithium salt is one of lithium hydroxide, lithium carbonate, lithium nitrate and lithium oxalate.
3. The method according to claim 2, wherein the lithium salt is lithium oxalate.
4. The method for preparing the in-situ coated single-crystal high-nickel ternary cathode material as claimed in claim 1, wherein in the step (2), the molar ratio of metal ions vanadium and metal ions molybdenum in the vanadium-containing flux and the molybdenum-containing flux in the mixed powder b is1: 1; the vanadium-containing fluxing agent is vanadium (V) oxide2O3) Vanadium pentoxide (V)2O5) Or ammonium metavanadate (NH)4VO3) (ii) a The molybdenum-containing fluxing agent is molybdenum oxide (MoO)3) Or ammonium molybdate ((NH)4)2MoO4)。
5. The method for preparing the in-situ coated single crystal high-nickel ternary cathode material as claimed in claim 1, wherein in the step (2), other fluxing agents are added into the mixed powder b, and the other fluxing agents are potassium fluoride (KF) and calcium chloride (CaCl)2) Lithium chloride (LiCl), lead oxide (PbO), boron oxide (B)2O3) And sodium chloride (NaCl); the mass fraction of the other fluxing agents is 10-50% of the mixed powder b.
6. The method for preparing the in-situ coated single crystal high-nickel ternary cathode material as claimed in claim 1, wherein in the step (3), the mixed powder c is heated to 160 ℃ at a heating rate of 5 ℃/min and is kept at the temperature for 2h in an oxygen atmosphere, is heated to 450 ℃ at a heating rate of 5 ℃/min and is kept at the temperature for 5h, is heated to 880 ℃ at a heating rate of 1 ℃/min and is kept at the temperature for 16h, and is cooled with a furnace to obtain a solid block material.
7. The method for preparing an in-situ coated single crystal high-nickel ternary cathode material as claimed in claim 1, wherein in the step (3), the solid bulk material is crushed and ground and then mixed with deionized water in a ratio of 1: 10, ultrasonically dispersing for 5min, then quickly filtering, and then placing in an air drying oven at 120 ℃ for drying for 2 h.
8. The lithium ion battery is characterized in that the in-situ coated single crystal high-nickel ternary cathode material prepared by the preparation method of any one of claims 1 to 7 is adopted as the cathode material of the lithium ion battery.
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