CN117164019A - Lithium-rich manganese-based positive electrode material and preparation method and application thereof - Google Patents
Lithium-rich manganese-based positive electrode material and preparation method and application thereof Download PDFInfo
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 57
- 239000011572 manganese Substances 0.000 title claims abstract description 57
- 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
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052796 boron Inorganic materials 0.000 claims abstract description 29
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 17
- 238000000975 co-precipitation Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010937 tungsten Substances 0.000 claims abstract description 15
- 239000012266 salt solution Substances 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000010405 anode material Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002585 base Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229910052810 boron oxide 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
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 18
- 238000006138 lithiation reaction Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 238000002955 isolation Methods 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000001639 boron compounds Chemical class 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910018553 Ni—O Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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 provides a lithium-rich manganese-based positive electrode material, and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Mixing a nickel source, a manganese source and a boron source with a solvent to obtain a mixed salt solution, and adding the mixed salt solution, alkali liquor and ammonia water into a base solution in parallel flow for coprecipitation reaction to obtain a boron doped anode precursor; (2) Calcining the boron doped anode precursor to obtain an oxide; (3) And mixing the oxide, the tungsten source and the lithium source, and performing sintering treatment to obtain the lithium-rich manganese-based anode material. According to the invention, the B element is added in the coprecipitation process, so that the B element can be uniformly distributed in the crystal, and the structural stability of the material is enhanced; by doping W element in the lithiation calcination stage, an isolation layer is formed on the particle surface during calcination, so that side reactions in the charge and discharge processes are reduced, and the cycle performance of the material is improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a lithium-rich manganese-based positive electrode material, and a preparation method and application thereof.
Background
Lithium-rich manganese-based xLi 2 MnO 3 ·(1-x)LiMO 2 The material has the characteristics of high capacity (the actual discharge capacity exceeds 250 mAh/g) and high voltage, so that the material becomes a hot point for research and development at home and abroad. Commercially available polycrystalline anodes allow penetration of liquid electrolyte into their internal structure, thereby increasing the reaction sites, but are prone to significant capacity fade and safety problems during long-term cycling.
The micron-sized monocrystalline material not only can effectively relieve surface interface side reactions in the electrochemical process by reducing the specific surface area, but also can help to improve the compaction density of the positive electrode due to the reduction of the porosity in the particle aggregation process, and shows higher lithium ion diffusion coefficient.
CN109956505a discloses a lithium-rich manganese-based positive electrode material, and a preparation method and application thereof, wherein the lithium-rich manganese-based positive electrode material is a flexible lithium-rich manganese-based positive electrode material, and does not contain other inert components, so that the energy density of the lithium-rich manganese-based positive electrode material is obviously improved.
CN113823786a discloses a preparation method of a modified lithium-rich manganese-based positive electrode material, and the single crystal fast lithium ion conductor coated lithium-rich manganese-based positive electrode material is obtained by performing single crystal and surface coating treatment simultaneously through a ball milling method.
A disadvantage of the single-crystal positive electrode material according to the above-described scheme is Li + The diffusion path is prolonged, leading to Li + Uneven distribution, after long-term cycling at high voltage or high current density, eventually leads to cracking inside the crystal. In addition, when the positive electrode is cycled in a highly delithiated state, it undergoes an irreversible phase change from H2 to H3, resulting in abrupt shrinkage of the lattice and the creation of nano-cracks, which decay in capacity once cracks begin to occur.
Disclosure of Invention
The invention aims to provide a lithium-rich manganese-based positive electrode material, a preparation method and application thereof. The B element is uniformly doped in the monocrystal, so that the interlayer distance is enlarged, lithium ion transmission is facilitated, and a stable crystal structure is realized; by doping the W element, a stable interface is formed, and gas production and structural collapse caused by the reaction of the oxygen-containing component and the electrolyte are relieved. Good rate performance and long-cycle stability can be realized through material modification.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a lithium-rich manganese-based cathode material, the method comprising the steps of:
(1) Mixing a nickel source, a manganese source and a boron source with a solvent to obtain a mixed salt solution, and adding the mixed salt solution, alkali liquor and ammonia water into a base solution in parallel flow for coprecipitation reaction to obtain a boron doped anode precursor;
(2) Calcining the boron doped anode precursor to obtain an oxide;
(3) And mixing the oxide, the tungsten source and the lithium source, and performing sintering treatment to obtain the lithium-rich manganese-based anode material.
According to the invention, the B element is added in the coprecipitation process, so that the B element can be uniformly distributed in the crystal, and the structural stability of the material is enhanced; by doping W element in the lithiation calcination stage, an isolation layer is formed on the particle surface during calcination, so that side reactions in the charge and discharge processes are reduced, and the cycle performance of the material is improved.
Preferably, the nickel source of step (1) comprises any one or a combination of at least two of nickel chloride, nickel sulfate or nickel nitrate.
Preferably, the manganese source comprises any one or a combination of at least two of manganese chloride, manganese sulfate or manganese nitrate.
Preferably, the boron source comprises boron oxide and/or boric acid.
Preferably, the molar ratio of the total molar amount of the nickel source and the manganese source to the boron element in the boron source is (99.5-99.98): (0.02-0.5), for example: 99.98:0.02, 99.95:0.05, 99.9:0.1, 99.7:0.3 or 99.5:0.5, etc.
Preferably, the total molar concentration of nickel and manganese in the mixed salt solution of step (1) is 1 to 3mol/L, for example: 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, etc.
Preferably, the lye comprises sodium hydroxide solution and/or potassium hydroxide solution.
Preferably, the concentration of the lye is 8 to 10mol/L, for example: 8mol/L, 8.5mol/L, 9mol/L, 9.5mol/L, 10mol/L, etc.
Preferably, the concentration of the ammonia water is 8 to 10mol/L, for example: 8mol/L, 8.5mol/L, 9mol/L, 9.5mol/L, 10mol/L, etc.
Preferably, the temperature of the coprecipitation reaction in step (1) is 40 to 80 ℃, for example: 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃ and the like.
Preferably, the pH of the coprecipitation reaction is 8 to 12, for example: 8. 9, 10, 11 or 12, etc.
Preferably, the temperature of the calcination treatment in step (2) is 600 to 950 ℃, for example: 600 ℃, 700 ℃, 800 ℃, 900 ℃ or 950 ℃ and the like.
Preferably, the calcination treatment is for 6 to 10 hours, for example: 6h, 7h, 8h, 9h or 10h, etc.
Preferably, the tungsten source of step (3) comprises WO 3 。
Preferably, the molar ratio of oxide to tungsten source is 100 (0.02 to 0.5), for example: 100:0.02, 100:0.05, 100:0.1, 100:0.3, or 100:0.5, etc.
Preferably, the lithium source comprises lithium hydroxide and/or lithium carbonate.
Preferably, the sintering treatment in step (3) is performed at a temperature of 900 to 1000 ℃, for example: 900 ℃, 920 ℃, 950 ℃, 980 ℃ or 1000 ℃ and the like.
Preferably, the sintering treatment is performed for a period of time ranging from 6 to 10 hours, for example: 6h, 7h, 8h, 9h or 10h, etc.
In a second aspect, the present invention provides a lithium-rich manganese-based cathode material, prepared by the method according to the first aspect.
In the lithium-rich manganese-based positive electrode material, B occupies the tetrahedral gap position of the filling oxygen crystal lattice to form stronger B-O covalent bond, the migration channel of transition metal ions is blocked, the uniform distribution of B elements in the crystal can realize an ideal stable structure, and serious lattice mismatch between a bulk phase and a surface and accumulation of microstress strain in crystal grains caused by concentration gradient distribution of lithium ions in micron-sized single crystals are effectively relieved. W is added together with a lithium source during lithiation and calcination, a synthesis process is not additionally added, W can react with the lithium source in the heat treatment process, a LWO layer is formed on the surface of the monocrystal, the mechanical strength is improved, charge aggregation around W is greater than Ni, a W-O bond stronger than Ni-O is formed, an interface is strengthened, and the surface stability is improved.
In a third aspect, the present invention provides a positive electrode sheet comprising the lithium-rich manganese-based positive electrode material according to the second aspect.
In a fourth aspect, the present invention provides a lithium ion battery comprising the positive electrode sheet according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention aims at the action principle of doping elements, and doping is respectively carried out through a coprecipitation stage and a calcination stage, so that the effect of doping modification is exerted to the greatest extent. The B element is uniformly doped in the monocrystal, so that the interlayer distance is enlarged, lithium ion transmission is facilitated, and a stable crystal structure is realized; by doping the W element, a stable interface is formed, and gas production and structural collapse caused by the reaction of the oxygen-containing component and the electrolyte are relieved. Good rate performance and long-cycle stability can be realized through material modification.
(2) The capacity retention rate of the lithium-rich manganese-based positive electrode material prepared into the battery 1C for 500 circles can reach more than 97.5%, the specific discharge capacity of 0.5C can reach more than 255.1mAh/g, the specific discharge capacity of 1C can reach more than 245.6mAh/g, the specific discharge capacity of 2C can reach more than 226.3mAh/g, the specific discharge capacity of 5C can reach more than 210.5mAh/g, the specific discharge capacity of 10C can reach more than 187.1mAh/g, the co-doping of a proper amount of metal W and nonmetal B can stabilize the material structure to improve the transmission of lithium ions, the material performance is judged by preparing different lithium-rich manganese-based positive electrode materials, the test is simple and convenient, and the reliability of the result is high, so that the best performance under W and B adopting proper doping amount is proved.
Drawings
Fig. 1 is an SEM image of a lithium-rich manganese-based positive electrode material according to example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a lithium-rich manganese-based positive electrode material, and the preparation method of the lithium-rich manganese-based positive electrode material comprises the following steps:
(1) According to the stoichiometric ratio Ni: mn: preparing a mixed salt solution from nickel salt, manganese salt and boron compound in a ratio of B=0.249:0.75:0.001, preparing 10mol/L of liquid alkali solution and 9mol/L of ammonia water, respectively adding the mixed salt solution, the alkali solution and the ammonia water into a reaction kettle through a metering pump under the protection of nitrogen, performing coprecipitation reaction under the conditions of 45 ℃ and pH value of 11, stopping feeding when the average grain size of materials in the reaction kettle reaches 4 mu m, centrifugally washing the solution in the reaction kettle, and drying to obtain a B-doped lithium-rich manganese-based anode precursor;
(2) Placing the prepared precursor in a calciner for calcination at a high temperature of 650 ℃ for 6 hours to obtain a corresponding oxide;
(3) The precursor oxide and WO 3 And the lithium source is mixed with the oxide W according to the mol ratio of Li=1:0.001:1.15 at a high speed, and then calcined in a sintering furnace at 970 ℃ for 8 hours, so that the lithium-rich manganese-based anode material is obtained. An SEM image of the lithium-rich manganese-based positive electrode material is shown in fig. 1.
Example 2
The embodiment provides a lithium-rich manganese-based positive electrode material, and the preparation method of the lithium-rich manganese-based positive electrode material comprises the following steps:
(1) According to the stoichiometric ratio Ni: mn: b=0.2498:0.75:0.0002, preparing a mixed salt solution from nickel salt, manganese salt and boron compound, preparing 9mol/L of aqueous alkali and 8mol/L of ammonia water, respectively adding the mixed salt solution, the aqueous alkali and the ammonia water into a reaction kettle through a metering pump under the protection of nitrogen, performing coprecipitation reaction at 45 ℃ and pH of 11, stopping feeding when the average particle size of materials in the reaction kettle reaches 4 mu m, centrifugally washing the solution in the reaction kettle, and drying to obtain a B-doped lithium-rich manganese-based anode precursor;
(2) Placing the prepared precursor in a calciner for calcination at a high temperature of 600 ℃ for 6 hours to obtain a corresponding oxide;
(3) The precursor oxide and WO 3 And the lithium source is mixed with the oxide W according to the mol ratio of Li=1:0.0002:1.12 at a high speed, and then calcined in a sintering furnace at 900 ℃ for 10 hours, so as to obtain the lithium-rich manganese-based anode material.
Example 3
The embodiment provides a lithium-rich manganese-based positive electrode material, and the preparation method of the lithium-rich manganese-based positive electrode material comprises the following steps:
(1) According to the stoichiometric ratio Ni: mn: preparing a mixed salt solution from nickel salt, manganese salt and a boron compound in a ratio of B=0.245:0.75:0.005, preparing 10mol/L aqueous alkali and 9mol/L ammonia water, respectively adding the mixed salt solution, the aqueous alkali and the ammonia water into a reaction kettle through a metering pump under the protection of nitrogen, performing coprecipitation reaction at 45 ℃ and pH of 11, stopping feeding when the average grain size of materials in the reaction kettle reaches 4 mu m, centrifugally washing the solution in the reaction kettle, and drying to obtain a B-doped lithium-rich manganese-based anode precursor;
(2) Placing the prepared precursor in a calciner for calcination at a high temperature of 950 ℃ for 6 hours to obtain a corresponding oxide;
(3) The precursor oxide and WO 3 And the lithium source is mixed with the oxide W according to the mol ratio of Li=1:0.001:1.15 at a high speed, and then calcined in a sintering furnace at 1000 ℃ for 6 hours, so as to obtain the lithium-rich manganese-based anode material.
Example 4
This example differs from example 1 only in that the molar ratio of the total molar amounts of the nickel source and the manganese source to the boron element in the boron source is 99:1, and other conditions and parameters are exactly the same as in example 1.
Example 5
This example differs from example 1 only in that the molar ratio of the total molar amounts of the nickel source and the manganese source to the boron element in the boron source is 99.99:0.01, and other conditions and parameters are exactly the same as in example 1.
Example 6
This example differs from example 1 only in that the molar ratio of oxide to tungsten source is 99:1, the other conditions and parameters being exactly the same as example 1.
Example 7
This example differs from example 1 only in that the molar ratio of oxide to tungsten source is 99.99:0.01, the other conditions and parameters being exactly the same as example 1.
Comparative example 1
This comparative example differs from example 1 only in that boron and tungsten are directly doped by co-precipitation, and other conditions and parameters are exactly the same as example 1.
Comparative example 2
This comparative example differs from example 1 only in that no boron source was added, and other conditions and parameters were exactly the same as example 1.
Example 3
This comparative example differs from example 1 only in that no tungsten source was added, and other conditions and parameters were exactly the same as example 1.
Performance test:
the first-week charge-discharge specific capacity and the cycle performance use a constant-current charge-discharge mode to charge and discharge the button cell at room temperature. The positive electrode material is assembled into a CR2025 rechargeable battery, and the charging and discharging cycle is carried out for 100 circles at 25 ℃ under the voltage range of 2.5V-4.6V and 1C/1C. The rate performance test method comprises the following steps: the rate performance of the cells was tested using 0.5C,1C,2C,5C and 10C current densities. The test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the battery 1C prepared from the lithium-rich manganese-based positive electrode material according to the invention has a capacity retention rate of 97.5% or more in 500 cycles, a specific 0.5C discharge capacity of 255.1mAh/g or more, a specific 1C discharge capacity of 245.6mAh/g or more, a specific 2C discharge capacity of 226.3mAh/g or more, a specific 5C discharge capacity of 210.5mAh/g or more, and a specific 10C discharge capacity of 187.1mAh/g or more, and the B, W co-doped lithium-rich manganese-based positive electrode material in a staged suitable range of the invention shows excellent capacity retention rate and rate capability.
As can be seen from comparison of examples 1 and 4-5, in the lithium-rich manganese-based positive electrode material of the present invention, the doping amount of boron affects the performance, and in the preparation process, the molar ratio of the total molar amount of the nickel source and the manganese source to the boron element in the boron source is controlled to be (99.5-99.98): (0.02-0.5), and the lithium-rich manganese-based positive electrode material has good performance, and if the doping amount of boron is too large, the transition substitution of boron in the crystal structure affects the exertion of the transition metal capacity, even causes lattice distortion; if the boron doping amount is too small, the effect of widening the lithium ion channel cannot be achieved, the diffusion and migration of the lithium ions are not obviously improved, and the capacity is limited.
As can be seen from comparison of the embodiment 1 and the embodiments 6-7, in the lithium-rich manganese-based positive electrode material, the doping amount of tungsten can influence the performance of the material, the molar ratio of oxide to tungsten source is controlled to be 100 (0.02-0.5) in the preparation process, the performance of the lithium-rich manganese-based positive electrode material is better, if the doping amount of tungsten is too large, the internal resistance of the crystal can be increased instead, the cycle performance of the material is deteriorated, and the rate performance is also deteriorated; if the tungsten doping amount is too small, enough W is not diffused to the surface layer of the crystal to form a stable isolation layer, and the effect of improving the cycle performance is not achieved.
As can be obtained by comparing the example 1 with the comparative example 1, the invention can uniformly distribute the B element in the crystal by adding the B element in the coprecipitation process, thereby enhancing the structural stability of the material; by doping W element in the lithiation calcination stage, an isolation layer is formed on the particle surface during calcination, so that side reactions in the charge and discharge processes are reduced, and the cycle performance of the material is improved.
As can be seen from comparison of the embodiment 1 and the comparative examples 2-3, in the lithium-rich manganese-based positive electrode material, B occupies the tetrahedral gap position of the filling oxygen crystal lattice, forms a stronger B-O covalent bond, blocks the migration channel of transition metal ions, ensures that the uniform distribution of B elements in the crystal can realize an ideal stable structure, and effectively relieves the serious lattice mismatch between the bulk phase and the surface caused by the concentration gradient distribution of lithium ions in the micron-sized single crystal and the accumulation of microstress strain in crystal grains. W is added together with a lithium source during lithiation and calcination, a synthesis process is not additionally added, W can react with the lithium source in the heat treatment process, a LWO layer is formed on the surface of the monocrystal, the mechanical strength is improved, charge aggregation around W is greater than Ni, a W-O bond stronger than Ni-O is formed, an interface is strengthened, and the surface stability is improved.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. The preparation method of the lithium-rich manganese-based positive electrode material is characterized by comprising the following steps of:
(1) Mixing a nickel source, a manganese source and a boron source with a solvent to obtain a mixed salt solution, and adding the mixed salt solution, alkali liquor and ammonia water into a base solution in parallel flow for coprecipitation reaction to obtain a boron doped anode precursor;
(2) Calcining the boron doped anode precursor to obtain an oxide;
(3) And mixing the oxide, the tungsten source and the lithium source, and performing sintering treatment to obtain the lithium-rich manganese-based anode material.
2. The method of claim 1, wherein the nickel source of step (1) comprises any one or a combination of at least two of nickel chloride, nickel sulfate, or nickel nitrate;
preferably, the manganese source comprises any one or a combination of at least two of manganese chloride, manganese sulfate or manganese nitrate;
preferably, the boron source comprises boron oxide and/or boric acid;
preferably, the molar ratio of the total molar amount of the nickel source and the manganese source to the boron element in the boron source is (99.5-99.98): 0.02-0.5.
3. The production method according to claim 1 or 2, wherein the total molar concentration of nickel and manganese in the mixed salt solution of step (1) is 1 to 3mol/L;
preferably, the lye comprises sodium hydroxide solution and/or potassium hydroxide solution;
preferably, the concentration of the alkali liquor is 8-10 mol/L;
preferably, the concentration of the ammonia water is 8-10 mol/L.
4. A process according to any one of claims 1 to 3, wherein the temperature of the coprecipitation reaction in step (1) is from 40 to 80 ℃;
preferably, the pH of the coprecipitation reaction is 8 to 12.
5. The method according to any one of claims 1 to 4, wherein the temperature of the calcination treatment in step (2) is 600 to 950 ℃;
preferably, the calcination treatment is performed for a period of 6 to 10 hours.
6. As claimed inThe process of any one of claims 1 to 5, wherein the tungsten source of step (3) comprises WO 3 ；
Preferably, the molar ratio of the oxide to the tungsten source is 100 (0.02-0.5);
preferably, the lithium source comprises lithium hydroxide and/or lithium carbonate.
7. The method of any one of claims 1-6, wherein the sintering process in step (3) is performed at a temperature of 900 to 1000 ℃;
preferably, the sintering treatment is performed for a period of 6 to 10 hours.
8. A lithium-rich manganese-based cathode material, characterized in that it is produced by the method according to any one of claims 1 to 7.
9. A positive electrode sheet comprising the lithium-rich manganese-based positive electrode material according to claim 8.
10. A lithium ion battery comprising the positive electrode sheet of claim 9.
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