WO2021088643A1 - 一种锂离子电池正极复合材料及其制备方法 - Google Patents
一种锂离子电池正极复合材料及其制备方法 Download PDFInfo
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- WO2021088643A1 WO2021088643A1 PCT/CN2020/122366 CN2020122366W WO2021088643A1 WO 2021088643 A1 WO2021088643 A1 WO 2021088643A1 CN 2020122366 W CN2020122366 W CN 2020122366W WO 2021088643 A1 WO2021088643 A1 WO 2021088643A1
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- lithium
- positive electrode
- composite material
- cobalt phosphate
- matrix
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- 239000002131 composite material Substances 0.000 title claims abstract description 76
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims abstract description 76
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims abstract description 72
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 71
- 239000011159 matrix material Substances 0.000 claims abstract description 70
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000007774 positive electrode material Substances 0.000 claims abstract description 42
- 230000002950 deficient Effects 0.000 claims abstract description 35
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 68
- 238000010438 heat treatment Methods 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 21
- 239000011247 coating layer Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 12
- 239000010406 cathode material Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229920008712 Copo Polymers 0.000 claims description 2
- ODLZNCJBFHAKOK-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Co+2].[Li+].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Co+2].[Li+].[Li+] ODLZNCJBFHAKOK-UHFFFAOYSA-K 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000005253 cladding Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 18
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 17
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000010452 phosphate Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CNGGOAOYPQGTLH-UHFFFAOYSA-N [O-2].[O-2].[Mg+2].[Al+3] Chemical compound [O-2].[O-2].[Mg+2].[Al+3] CNGGOAOYPQGTLH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229940074545 sodium dihydrogen phosphate dihydrate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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Definitions
- the invention belongs to the technical field of lithium ion batteries, and in particular relates to a lithium ion battery cathode composite material and a preparation method thereof.
- the methods of using cobalt phosphate to coat positive electrode materials in the prior art mainly include: (1) adding the positive electrode material to the soluble cobalt salt solution, then adding the soluble phosphate solution, and performing heat treatment after mixing uniformly; (2) combining the soluble cobalt salt with The phosphate solution is mixed, and then the positive electrode material is added, and the heat treatment is performed after uniform mixing; (3) The soluble cobalt salt solution is mixed with the soluble phosphate solution to obtain micron-level large particles, which are mixed with the positive electrode material and then heat treated.
- the above preparation methods because the soluble cobalt salt and phosphate will quickly generate micron-sized particles after mixing, the cobalt phosphate cannot be fully mixed with the matrix material uniformly, and the cobalt phosphate cannot uniformly coat the positive electrode material during the heat treatment process.
- the problem of the substrate In addition, the above preparation methods all use liquid phase coating.
- the solvent used in the liquid phase coating process will also corrode the surface of the positive electrode material, causing the surface structure of the positive electrode material to be destroyed, and it is easy to cause excessive capacity loss at the first time. problem.
- the technical problem to be solved by the present invention is to provide a lithium ion battery cathode material and a preparation method thereof in order to overcome the shortcomings and defects mentioned in the above background art.
- a lithium-ion battery cathode composite material comprising a lithium-containing matrix and a three-layer coating layer covering the surface of the substrate.
- the three-layer coating layers are respectively a lithium-deficient matrix material layer and a lithium-deficient matrix material layer from the inside to the outside.
- Lithium cobalt phosphate lithium layer and cobalt phosphate layer.
- the design idea of the above technical scheme is: by covering the surface of the positive electrode material substrate with a lithium-deficient matrix material layer, a lithium-deficient lithium cobalt phosphate layer and a cobalt phosphate layer from the inside to the outside, because the outer layer is coated with a coating that does not contain high-valent cobalt
- the layer reduces the oxidation of the tetravalent cobalt in the high-de-lithium positive electrode material under high voltage to the electrolyte, avoids the formation of an inert film at the interface between the material and the electrolyte, worsens the interface environment, and reduces the performance of the positive electrode material; at the same time, the above-mentioned positive electrode composite material
- the three coating layers are all composed of high-voltage materials, and the discharge voltage during charging and discharging can be higher than that of the uncoated positive electrode material, and the battery prepared by it will have a higher energy density.
- the lithium-containing matrix is a layered lithium composite oxide
- the chemical formula is Li a Co 1-b M b O 2
- M is one or more of Mg, Al, Ti, Zr and W Species, 0.95 ⁇ a ⁇ 1.1, 0.0 ⁇ b ⁇ 0.01.
- Selecting the matrix as a layered lithium composite oxide can ensure that the matrix further reacts with the cobalt phosphate to form a lithium-deficient lithium cobalt phosphate to form an inner lithium-deficient matrix material layer, which makes the three-layer coating structure easier to form, which is beneficial The stability of the overall structure.
- the chemical formula of the matrix lithium-deficient matrix material layer is Li c Co 1-b M b O 2 , and M is one or more of Mg, Al, Ti, Zr and W, 0.0 ⁇ c ⁇ 1.0, 0.0 ⁇ b ⁇ 0.01.
- the chemical formula of the lithium-deficient lithium cobalt phosphate layer is Li d CoPO 4 , 0.0 ⁇ d ⁇ 1.0.
- the design idea here is to choose the cobalt phosphate layer with the chemical formula Co m (PO 4 ) n , there will be no tetravalent Co after delithiation, avoiding the contact between tetravalent cobalt and the electrolyte, and its potential It is higher than lithium cobalt oxide, which helps to increase the discharge voltage.
- the thickness of the lithium-deficient lithium cobalt phosphate layer does not exceed 10 nm, and the thickness of the cobalt phosphate layer does not exceed 10 nm.
- the D50 particle size of the positive electrode composite material ranges from 6 to 23 microns.
- a method for preparing a positive electrode composite material according to any one of the above technical solutions including the following steps:
- the design idea of the above technical scheme is: by mixing the cobalt phosphate and the lithium-containing matrix, the cobalt phosphate is uniformly adsorbed on the surface of the lithium-containing matrix. After heat treatment, part of the cobalt phosphate exists in the outermost layer in the form of anhydrous cobalt phosphate.
- the cobalt phosphate reacts with the remaining LiOH, Li 2 CO 3 or LiHCO 3 on the surface of the lithium-containing substrate to obtain lithium cobalt phosphate in a lithium-deficient state, and the lithium-deficient lithium cobalt phosphate further reacts with the positive electrode material matrix to obtain part of the extracted lithium
- the matrix material layer of ions forms a three-layer coating structure on the surface of the positive electrode material.
- the heat treatment temperature is 900-1100° C.
- the heat treatment time is 6-20 h.
- the heat treatment temperature in the step (2) is 400-900°C.
- the heat treatment temperature is 400 to 600°C, and the heat treatment time
- the heat treatment temperature is 600-800°C, and the heat treatment time is 5-9h
- the heat treatment temperature is 800 to 900° C., and the heat treatment time is 7 to 9 hours.
- the idea of this design is to determine the temperature and time range of the heat treatment based on the ratio of cobalt phosphate to the mass of the matrix, and heat the mixture to obtain a positive electrode composite material.
- Increasing the temperature and time of the heat treatment will increase the degree of reaction between the cobalt phosphate and the residual lithium compound on the surface of the substrate and the degree of reaction between the lithium cobalt phosphate in the lithium-deficient state and the substrate, thereby adjusting the corresponding thickness of the three layers.
- the designed heat treatment temperature is higher and the time is longer.
- the degree of reaction between the cobalt phosphate and the residual lithium compound on the surface of the matrix and the lithium-deficient cobalt phosphate can be more accurately controlled The degree of reaction between the lithium and the substrate, so as to obtain the positive electrode composite material with the thickness of the three-layer coating layer that meets the expected design, so that the positive electrode composite material has the stability of the electrolyte under high voltage, and it will not be affected by the thickness of the coating layer. Too thick, resulting in a decrease in specific capacity.
- the particle size of the cobalt phosphate is 5 to 200 nm.
- the purpose of this design is to reduce the probability that cobalt phosphate is adsorbed on the surface of the positive electrode material matrix in block form by selecting nano-scale cobalt phosphate as the coating material, so that the cobalt phosphate is more uniformly distributed. It is also conducive to forming a coating layer with the same structure, uniform thickness and even distribution.
- the outer layer of the positive electrode composite material of the present invention is coated with a coating layer that does not contain high-valence cobalt, which reduces the oxidation effect of the high-delithiation positive electrode material on the electrolyte under high voltage, and the three coating layers are uniform Composed of high-voltage materials, the discharge voltage during charging and discharging is higher than that of the uncoated positive electrode material, and it has a higher energy density.
- the preparation method of the positive electrode composite material of the present invention uses dry method and heat treatment to coat the positive electrode material, which avoids the possible erosion of the surface of the positive electrode material by the liquid phase coating under the same effect and the resulting reduction in electrochemical performance
- the problem is that the obtained coating layer has a uniform thickness and stable properties.
- Figure 1 is a TEM image of nano cobalt phosphate
- Figure 2 is a TEM image of the nano-cobalt phosphate mixed with the matrix
- Figure 3 is a TEM image of nano-cobalt phosphate and matrix after mixed heat treatment
- Figure 4 shows the XRD images of nano cobalt phosphate before and after heat treatment
- Figure 5 is a TEM image of a cross section of the cathode composite material
- Figure 6a is the XPS test spectrum of Li element
- Figure 6b is the XPS test spectrum of P element
- Fig. 7 is a schematic diagram of a mixture of cobalt phosphate and positive electrode material before and after heat treatment
- FIG. 8 is a charge-discharge curve diagram of the positive electrode composite material of Example 1;
- Figure 9 shows the cycle performance of the positive electrode materials of Example 5 and Comparative Example 1;
- Example 10 is a graph showing the average discharge voltage of different turns of the positive electrode composite material of Example 2.
- Example 11 is an electron microscope image of the positive electrode composite material of Example 5 and an electron microscope image of the positive electrode composite material prepared by a conventional method in Comparative Example 2.
- the various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or can be prepared by existing methods.
- a cathode composite material for lithium ion batteries with a D50 particle size range of 10-11 microns is composed of a layered lithium composite oxide matrix with a chemical formula of Li 1.01 Co 0.995 Al 0.003 Mg 0.002 O 2 and coated on the surface of the substrate
- the three coating layers are composed of a lithium-deficient matrix material layer, a lithium-deficient lithium cobalt phosphate layer, and a cobalt phosphate layer with a chemical formula of Co 3 (PO 4 ) 2 .
- the thickness of the cobalt phosphate layer is 3-5 nanometers, and the thickness of the lithium-deficient lithium cobalt phosphate layer is 4-9 nanometers.
- a method for preparing the above-mentioned positive electrode composite material includes the following steps:
- the morphology of the added nano cobalt phosphate is shown in Figure 1. It can be clearly seen that the cobalt phosphate particles are nano-agglomerated, and the morphology of the nano cobalt phosphate and lithium cobaltate matrix after being mixed (before heat treatment) is shown in Figure 1. As shown in 2, it can be clearly seen that the nano-cobalt phosphate adsorbs to the surface of the substrate relatively uniformly, and the distribution is very uniform.
- the XRD pattern of the nano cobalt phosphate after heat treatment is shown in Figure 4, and it can be seen that the structure of the nano cobalt phosphate has not changed much after the heat treatment.
- the positive electrode composite material prepared in this embodiment was subjected to acid etching treatment, and XPS was used to test the element content at different depths.
- the specific steps include the following: prepare a dilute hydrochloric acid solution with a concentration of 0.1 mol/L, take 10 g of LCO-A1 and soak in the solution for 1 min, rinse with deionized water, and dry in an oven at 80 °C, numbered LCO-A2; take 10 g of LCO-A1 , Immerse in the solution for 3 minutes, rinse with deionized water, and put it in an oven at 80°C for drying, numbered LCO-A3.
- a lithium-ion battery cathode composite material with a D50 particle size range of 19-20 microns The cathode composite material is composed of a layered lithium composite oxide matrix with a chemical formula of Li 1.01 Co 0.996 Al 0.002 Ti 0.001 Mn 0.001 O 2 and coated on
- the three-layer coating layer on the surface of the substrate is composed of a lithium-deficient substrate material layer, a lithium-deficient lithium cobalt phosphate layer, and a cobalt phosphate layer with a chemical formula of Co 3.5 (PO 4 ) 2 .
- the thickness of the cobalt phosphate layer is 3-5 nanometers, and the thickness of the lithium-deficient lithium cobalt phosphate layer is 3-6 nanometers.
- a method for preparing the above-mentioned positive electrode composite material includes the following steps:
- a lithium-ion battery cathode composite material with a D50 particle size range of 21-22 microns The cathode composite material is composed of a layered lithium composite oxide matrix with a chemical formula of Li 1.015 Co 0.995 Ti 0.001 Ca 0.002 Mn 0.002 O 2 and coated on
- the three-layer coating layer on the surface of the substrate is composed of a lithium-deficient substrate material layer, a lithium-deficient lithium cobalt phosphate layer, and a cobalt phosphate layer with a chemical formula of Co 2.8 (PO 4 ) 2 .
- the thickness of the cobalt phosphate layer is 4-6 nanometers, and the thickness of the lithium-deficient lithium cobalt phosphate layer is 6-10.
- a method for preparing the above-mentioned positive electrode composite material includes the following steps:
- the prismatic aluminum shell battery prepared by LCO-D0 and LCO-D1 was subjected to high-temperature storage performance test. The results are shown in Table 1. From the test results, it can be seen that the positive electrode composite material with the three-layer coating structure of this embodiment was prepared The increase in battery thickness of the battery at high temperature is significantly lower than that of a battery prepared from an uncoated positive electrode material under the same conditions. It can be seen that the positive electrode composite material of this embodiment has better high-temperature stability performance.
- a lithium ion battery cathode composite material with a D50 particle size range of 20-21 microns The cathode composite material is composed of a layered lithium composite oxide matrix with a chemical formula of Li 1.01 Co 0.996 Al 0.002 Ti 0.002 O 2 and coated on the surface of the substrate
- the three coating layers are composed of a lithium-deficient matrix material layer, a lithium-deficient lithium cobalt phosphate layer, and a cobalt phosphate layer with a chemical formula of Co 3 (PO4) 2 .
- the thickness of the cobalt phosphate layer is 5-9 nanometers, and the thickness of the lithium-deficient lithium cobalt phosphate layer is 6-10 nanometers.
- a method for preparing the above-mentioned positive electrode composite material includes the following steps:
- a lithium-ion battery cathode composite material with a D50 particle size range of 20-21 microns The cathode composite material is composed of a layered lithium composite oxide matrix with a chemical formula of Li 1.005 Co 0.995 Al 0.003 Mg 0.001 Ti 0.002 O 2 and coated on
- the three-layer coating layer on the surface of the substrate is composed of a lithium-deficient substrate material layer, a lithium-deficient lithium cobalt phosphate layer, and a cobalt phosphate layer with a chemical formula of Co 3 (PO 4 ) 2 .
- the thickness of the cobalt phosphate layer is 2-6 nanometers, and the thickness of the lithium-deficient lithium cobalt phosphate layer is 5-9 nanometers.
- a method for preparing the above-mentioned positive electrode composite material includes the following steps:
- a preparation method of positive electrode composite material :
- the first discharge capacity and cycle performance of LCO-B0, LCO-B1 and LCO-B2 were tested. The results are shown in Table 2 and Figure 9. It can be seen from Table 2 and Figure 9 that the purchased micron-level cobalt phosphate was used for the positive electrode material.
- the positive electrode composite material prepared by the coating has a large capacity loss when it is first used. Although its cycle stability is better than that of the non-coated positive electrode material, in comparison, the positive electrode material is coated with nano-cobalt phosphate
- the prepared positive electrode composite material ie, the positive electrode composite material of Example 4 has no loss of capacity for the first use under the same conditions, and the cycle performance is improved more obviously.
- a method for preparing the above-mentioned positive electrode composite material includes the following steps:
- LCO-F1 and LCO-F2 The morphology of LCO-F1 and LCO-F2 is shown in Figure 11. It can be seen from Figure 11 that, in the positive electrode composite material of Example 5, the phosphate is distributed and coated uniformly on the surface of the positive electrode material, while the composite prepared by conventional methods Most of the phosphate is attached to the surface of the positive electrode material in agglomerated state (the structure circled in Figure 11 is the agglomerated cobalt phosphate).
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Abstract
Description
LCO-D0 | LCO-D1 | |
85℃6h后电池厚度增加量(%) | 17.7 | 9.8 |
60℃7d后电池厚度增加量(%) | 45.2 | 26 |
LCO-B0 | LCO-B1 | LCO-B2 | |
首次容量(mAhg -1) | 211.2 | 211.0 | 209.9 |
Claims (10)
- 一种锂离子电池正极复合材料,其特征在于,包括含锂基体和包覆在基体表面的三层包覆层,所述三层包覆层由内至外分别为缺锂基体材料层、缺锂磷酸钴锂层和磷酸钴层。
- 如权利要求1所述的正极复合材料,其特征在于,所述含锂基体为层状锂复合氧化物,化学式为Li aCo 1-bM bO 2,M为Mg、Al、Ti、Zr和W中的一种或多种,0.95≤a≤1.1,0.0≤b≤0.01。
- 如权利要求1所述的正极复合材料,其特征在于,所述缺锂基体材料层的化学式为Li cCo 1-bM bO 2,M为Mg、Al、Ti、Zr和W中的一种或多种,0.0<c<1.0,a<c,0.0≤b≤0.01。
- 如权利要求1所述的正极复合材料,其特征在于,所述缺锂磷酸钴锂层的化学式为Li dCoPO 4,0.0<d<1.0。
- 如权利要求1所述的正极复合材料,其特征在于,所述磷酸钴层的化学式为Co m(PO 4) n,其中m/n=1.3~1.7。
- 如权利要求1所述的正极复合材料,其特征在于,所述缺锂磷酸钴锂层的厚度不超过10nm,所述磷酸钴层的厚度不超过10nm。
- 如权利要求1-6任一所述的正极复合材料,其特征在于,所述正极复合材料的D50粒径范围为6~23μm。
- 一种如权利要求1-7任一所述的正极复合材料的制备方法,其特征在于,包括以下步骤:(1)将正极材料前驱体和锂源混合后进行热处理6~20h,得到含锂基体;(2)将磷酸钴和含锂基体混合后进行热处理3~9h,得到正极复合材料,所述磷酸钴和正极材料基体的质量比为(0.005:1)~(0.5:1)。
- 如权利要求8所述的制备方法,其特征在于,所述步骤(2)中,磷酸钴和正极材料基体的质量比为(0.005:1)~(0.02:1)时,所述热处理温度为400~600℃,热处理时间为3~6h;磷酸钴和正极材料基体的质量比为(0.02:1)~(0.04:1)时,所述热处理温度为600~800℃,热处理时间为5~9h;当所述磷酸钴和正极材料基体的质量比为(0.04:1)~(0.05:1)时,所述热处理温度为800~900℃,热处理时间为7~9h。
- 如权利要求8~9任一所述的制备方法,其特征在于,所述磷酸钴粒径为5~200nm。
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