CN114864910B - Coated ternary material and application thereof - Google Patents
Coated ternary material and application thereof Download PDFInfo
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- CN114864910B CN114864910B CN202210672552.1A CN202210672552A CN114864910B CN 114864910 B CN114864910 B CN 114864910B CN 202210672552 A CN202210672552 A CN 202210672552A CN 114864910 B CN114864910 B CN 114864910B
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- 239000000463 material Substances 0.000 title claims abstract description 169
- 239000011247 coating layer Substances 0.000 claims abstract description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 16
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- 239000010937 tungsten Substances 0.000 claims description 13
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 9
- 229910013716 LiNi Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 238000005253 cladding Methods 0.000 abstract description 7
- 239000010410 layer Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- -1 tungsten ions Chemical class 0.000 description 10
- 238000002156 mixing Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Abstract
The invention provides a cladding ternary material and application thereof, wherein a cladding layer of the cladding ternary material comprises a WAO material, and the WAO material is tungsten oxide doped aluminum oxide. The invention adopts the tungsten oxide doped alumina material WAO as the coating layer of the ternary material, overcomes the problem of poor conductivity of the alumina coating layer, and combines W 6+ The WAO coating layer has good ion conductivity and electron conductivity, improves the lattice compatibility of the coating layer and the ternary material, and effectively improves the cycle stability and the multiplying power performance of the ternary material.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a ternary material, in particular to a coated ternary material and application thereof.
Background
The working voltage of the current commercial ternary material battery is about 4.2-4.35V, the utilization rate of reversible lithium is insufficient, and the charging voltage is required to be improved in order to further improve the volume energy density of the ternary battery. However, when the charging voltage exceeds 4.4V, the electrochemical performance of the battery will be drastically reduced due to thermodynamic instability of the layered structure in a highly delithiated state and degradation of the interface performance of the positive electrode/electrolyte due to surface side reactions, which is manifested as serious increase of gas production and significant increase of DCR (direct current internal resistance) during cycling.
The aluminum oxide coating is coated on the surface of the ternary material, so that the problems can be effectively solved, a compact aluminum oxide coating is formed on the surface of the coated ternary material, the side reaction of an electrode-electrolyte interface can be reduced to the greatest extent, and the impedance is increased during control cycle; however, the coating itself generally exhibits poor Li + Conductivity, and impedes surface charge transfer, which deteriorates cycle and rate performance.
Based on the above research, it is necessary to provide a coated ternary material, in which the coating layer has good electron conductivity, has good lattice compatibility with the ternary material, and can improve the cycle stability and rate capability of the material.
Disclosure of Invention
The invention aims to provide a coated ternary material and application thereof, wherein a coating layer of the coated ternary material is an alumina material, and tungsten oxide is doped in the alumina material, so that the electronic conductivity of the coating layer is improved, and the electrochemical performance of the ternary material is improved.
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 coated ternary material, wherein the coating layer of the coated ternary material comprises a WAO material, and the WAO material is tungsten oxide doped aluminum oxide.
The invention adopts the tungsten oxide doped alumina material WAO as the coating layer of the ternary material, overcomes the problem of poor conductivity of the alumina coating layer, and combines W 6+ The WAO coating layer has good ionic conductivity and electronic conductivity, improves the lattice compatibility of the coating layer and the ternary material, has the following advantages ofThe cycling stability and the multiplying power performance of the ternary material are effectively improved; wherein, in WAO material, W 6+ Ion-exchanged portion Al 3+ Ions, W in WAO materials, compared to simply mixed tungsten oxide and aluminum oxide materials 6+ The ions are uniformly distributed in the alumina crystal lattice, so that the alumina can achieve the purpose of improving the conductivity of the coating by means of the advantages of tungsten ions.
W in the WAO material represents tungsten element, and A represents aluminum element.
Preferably, the mass percent of the WAO material is 0.3wt% to 0.7wt%, based on the mass of the coated ternary material, and may be, for example, 0.3wt%, 0.35wt%, 0.4wt%, 0.45wt%, 0.5wt%, 0.55wt%, 0.6wt%, 0.65wt%, or 0.7wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The WAO material provided by the invention can simultaneously ensure that the ternary material has high energy density and good conductivity and dynamic performance in a reasonable coating amount range.
Preferably, in the WAO material, the mass ratio of Al element to W element is 1 (2 to 4), for example, it may be 1:2, 1:2.5, 1:3, 1:3.5 or 1:4, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the content of the Al element in the coated ternary material is 500ppm to 1500ppm, for example, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm, 1000ppm, 1100ppm, 1200ppm, 1300ppm, 1400ppm or 1500ppm, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the content of W element in the coated ternary material is 2400ppm to 3200ppm, for example 2400ppm, 2500ppm, 2600ppm, 2700ppm, 2800ppm, 2900ppm, 3000ppm, 3100ppm or 3200ppm, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
The invention can obtain a thin and uniform WAO coating layer on the surface of the ternary material particles by controlling the quantity and the element proportion of two oxides in the WAO material.
Preferably, the preparation raw materials of the coated ternary material comprise a ternary material primary product, a WAO material and a solvent.
Preferably, the solvent comprises ethanol.
According to the invention, a burned product of the ternary material is mixed with the WAO material, and the WAO material is uniformly coated on the surface of the ternary material by adopting ethanol as a solvent through wet coating; in addition, the wet coating is carried out by stirring in the solvent until the solvent is completely volatilized, so that the coating is more uniform than the dry coating.
According to the invention, the volatile ethanol is used as the solvent, so that the ternary material and the WAO material can be prevented from being damaged, and the influence of the residual solvent on the performance of the coated ternary material can be avoided.
Preferably, the core composition of the clad ternary material comprises LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.55 and less than or equal to 0.60,0.10, and y is more than or equal to 0.12.
The core body composition of the coated ternary material can be low in cost, high in safety and high in performance.
The core composition of the cladding ternary material comprises LiNi x Co y Mn 1-x-y O 2 Wherein 0.55.ltoreq.x.ltoreq.0.60, may be, for example, 0.55, 0.56, 0.57, 0.58, 0.59 or 0.60, but is not limited to the values recited, other values not recited in the numerical range being equally applicable.
The core composition of the cladding ternary material comprises LiNi x Co y Mn 1-x-y O 2 Wherein, 0.10.ltoreq.y.ltoreq.0.12, for example, 0.1, 0.105, 0.11, 0.115 or 0.12, but not limited to the values recited, other non-recited values within the numerical range are equally applicable.
The preparation method of the coated ternary material comprises the following steps:
mixing the ternary material I firing product, the WAO material and the solvent, stirring to volatilize the solvent completely, and sintering the obtained mixture to obtain the coated ternary material.
Preferably, the particle size of the WAO material is on the order of nanometers.
Preferably, the solvent is ethanol.
Preferably, the sintering temperature is 300 ℃ to 600 ℃, for example, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, or 600 ℃, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the sintering time is 10h to 18h, for example, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h or 18h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In a second aspect, the present invention is directed to an electrochemical device comprising a coated ternary material as described in the first aspect.
Preferably, the positive electrode sheet of the electrochemical device comprises the doped ternary material, the conductive agent and polyvinylidene fluoride in a mass ratio of (90 to 99): (0.1 to 7): 1, and may be, for example, 90:0.1:1, 92:1:1, 94:5:1 or 99:7:1, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the positive electrode current collector of the electrochemical device is an aluminum foil.
Preferably, the negative electrode sheet of the electrochemical device comprises graphite, conductive carbon black, sodium carboxymethyl cellulose and styrene-butadiene rubber in a mass ratio of (90 to 99): (0.1 to 2): (0.5 to 3): 2, and may be, for example, 90:1:1.5:2, 92:1:1.5:2, 94:2:3:2, or 99:0.1:0.5:2, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the negative electrode current collector of the electrochemical device is a copper foil.
In a third aspect, the present invention provides an electronic device comprising an electrochemical apparatus as described in the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the thin and uniform WAO coating layer is coated on the surface of the ternary material, and the problem of conductivity of the single-purity aluminum oxide coating layer is solved by means of tungsten ions in the WAO material, so that the coating layer has good ion conductivity and electronic conductivity, the lattice compatibility of the coating layer and the ternary material is improved, and the cycle stability and the multiplying power performance of the ternary material are effectively improved; the invention adopts wet coating, wherein a sintered product of ternary material is used for coating in the coating process, and after stirring to volatilize the solvent completely, the mixture is sintered, so that a uniform coating layer can be obtained.
Drawings
FIG. 1 is a tungsten ion back-scattering diagram of SEM of a coated ternary material according to example 1 of the invention;
fig. 2 is a tungsten ion back-scattering diagram of SEM of the coated ternary material of comparative example 3 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 cladding ternary material, the core composition of which is LiNi 0.58 Co 0.11 Mn 0.31 O 2 The coating layer is made of WAO material, and the WAO material is alumina doped with tungsten oxide;
based on the mass of the coated ternary material, the mass percentage of the WAO material is 0.54 weight percent, the content of the Al element is 1000ppm, and the content of the W element is 2800ppm;
in the WAO material, the mass ratio of the Al element to the W element is 1:3;
the preparation raw materials of the coated ternary material comprise a ternary material I-fired product, a WAO material and ethanol;
the preparation method of the coated ternary material comprises the following steps:
mixing the ternary material I firing product, WAO material and ethanol, stirring to volatilize the ethanol completely, and sintering the obtained mixture at 450 ℃ for 15 hours to obtain the coated ternary material, wherein a tungsten ion back scattering diagram of SEM is shown in figure 1;
the WAO material is doped with tungsten in the process of preparing alumina, so that the WAO material of tungsten oxide doped with alumina is obtained.
Example 2
The embodiment provides a coated ternary material, the core composition of which comprises LiNi 0.6 Co 0.12 Mn 0.28 O 2 The coating layer is made of WAO material, and the WAO material is alumina doped with tungsten oxide;
based on the mass of the coated ternary material, the mass percentage of the WAO material is 0.3wt%, the content of the Al element is 700ppm, and the content of the W element is 1400ppm;
in the WAO material, the mass ratio of the Al element to the W element is 1:2;
the preparation raw materials of the coated ternary material comprise a ternary material I-fired product, a WAO material and ethanol;
the preparation method of the coated ternary material comprises the following steps:
mixing the ternary material I firing product, the WAO material and the ethanol, stirring to volatilize the ethanol completely, and sintering the obtained mixture at 300 ℃ for 18 hours to obtain the coated ternary material;
the WAO material is doped with tungsten in the process of preparing alumina, so that the WAO material of tungsten oxide doped with alumina is obtained.
Example 3
The embodiment provides a coated ternary material, the core composition of which comprises LiNi 0.58 Co 0.11 Mn 0.31 O 2 The coating layer is made of WAO material, and the WAO material is alumina doped with tungsten oxide;
based on the mass of the coated ternary material, the mass percentage of the WAO material is 0.7wt%, the content of the Al element is 1000ppm, and the content of the W element is 4000ppm;
in the WAO material, the mass ratio of the Al element to the W element is 1:4;
the preparation raw materials of the coated ternary material comprise a ternary material I-fired product, a WAO material and ethanol;
the preparation method of the coated ternary material comprises the following steps:
mixing the ternary material I firing product, the WAO material and the ethanol, stirring to volatilize the ethanol completely, and sintering the obtained mixture at 600 ℃ for 10 hours to obtain the coated ternary material;
the WAO material is doped with tungsten in the process of preparing alumina, so that the WAO material of tungsten oxide doped with alumina is obtained.
The clad ternary materials provided in examples 4 and 5 are as shown in Table 2, except that the content of the Al element is changed, and the same as in example 1 is adopted.
The clad ternary materials provided in examples 6 and 7 are as shown in Table 3, except that the content of W element is changed, and the same as in example 1 is adopted.
The coated ternary materials provided in examples 8 and 9 are shown in Table 4, and are the same as example 1 except that the WAO material is changed in mass percent.
The coated ternary material provided in example 10 is shown in table 5, and the other materials are the same as in example 1 except that the coated ternary material is prepared from only the ternary material, i.e., the fired product and the WAO material, and the materials are coated by a dry method by simple mixing.
Comparative example 1 provides a ternary material having the same composition as the core composition described in example 1, and does not include a cladding layer.
The ternary material provided in comparative example 2 is shown in table 6, except that the coating layer of the ternary material is a simple alumina coating layer, and is the same as example 1.
The ternary material provided in comparative example 3 is shown in table 6, except that the coating layer of the ternary material is a mixed coating layer of alumina and oxide, the same as example 1; the tungsten ion back-scattering diagram of the ternary material SEM of this comparative example is shown in fig. 2.
Mixing the coated ternary material obtained in the above example and the ternary material obtained in the comparative example with conductive carbon black, carbon nanotubes and polyvinylidene fluoride in a mass ratio of 97:1:0.5:1, placing the mixture in an N-methylpyrrolidone solvent to prepare slurry, coating the slurry on an aluminum foil, drying, and rolling to obtain a positive plate; graphite, conductive carbon black, sodium carboxymethylcellulose and styrene-butadiene rubber with the mass ratio of 96:0.5:0.5:2 are coated on copper foil in an N-methylpyrrolidone solvent, and a negative plate is obtained after drying and rolling; and assembling the obtained positive plate, the polyethylene diaphragm and the lithium hexafluorophosphate electrolyte into a lithium ion battery.
According to the positive plate obtained by disassembling the lithium ion battery, the powder obtained by scraping the powder is tested by using an inductively coupled plasma method, and the elements and the content of the coated ternary material can be obtained.
Gram capacity test method: charging and discharging for one week in a charging and discharging mode of 0.063A/g at 25 ℃, wherein the cut-off voltage is 2.8-4.4V, and the obtained charge/discharge capacity is divided by the usage amount of the positive electrode, namely the first charge/discharge gram capacity; the test equipment was a Cheng Hong Electrical Co., ltd battery performance test system (equipment model: BTS05/10C 8D-HP).
The cyclic capacity retention test method: the lithium ion battery obtained above circulates in a charge-discharge system of 0.19A/g (calculated by the mass of the anode material) at 25 ℃, and after the circulation is completed for 800 weeks, the discharge capacity of the battery at the moment is divided by the discharge capacity of the battery at the first circle, namely the 800-circle circulation capacity retention rate of the battery; the test equipment was a Cheng Hong Electrical Co., ltd battery performance test system (equipment model: BTS05/10C 8D-HP).
The multiplying power capacity retention rate testing method comprises the following steps: charging and discharging for three weeks at 25deg.C in a charging and discharging system of 0.063A/g (0.33C), with a cutoff voltage of 2.8-4.4V, and recording the discharge capacity of the third week; then charging and discharging for one week by a charging and discharging system of 0.57A/g (3C), recording the discharge capacity and dividing the discharge capacity by the discharge capacity at 0.33C, namely the high-rate capacity retention rate of the battery; the test equipment was a Cheng Hong Electrical Co., ltd battery performance test system (equipment model: BTS05/10C 8D-HP).
The test results are shown in the following table:
TABLE 1
| 3C rate capacity retention (%) | 800 cycle capacity retention (%) | |
| Example 1 | 70 | 95 |
| Example 2 | 63 | 92 |
| Example 3 | 65 | 93 |
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 5
TABLE 6
From the above table it can be seen that:
(1) As can be seen from examples 1 to 10 and comparative examples 1 to 3, the present invention adopts WAO material as the coating layer, which can improve the conductivity of the coating layer, thereby improving the rate performance and cycle performance of the battery; as is clear from examples 1 and 4 to 9, the contents of Al element, W element and coating material are within a reasonable range, and the obtained coating layer can be made thin and uniform, thereby obtaining a ternary material excellent in comprehensive properties; as can be seen from examples 1 and 10, the present invention adopts wet coating, and the volatile ethanol is used as the coating solvent, so that the distribution of the coating material is more uniform than that of dry coating, thereby improving the comprehensive performance of the material.
(2) As can be seen from example 1 and comparative example 1, the WAO coating layer of the present invention can improve the rate and cycle performance of the battery; as can be seen from examples 1 and 2, the coating layer of the present invention can overcome the defect of using single pure alumina as the coating layer; as is clear from example 1 and comparative example 3, comparative example 3 uses a mixture of alumina and tungsten oxide as the coating layer, unlike the WAO coating layer of the present invention, W in the WAO material of the present invention 6+ The ions are uniformly distributed in the alumina crystal lattice, the dispersibility is good, and W 6+ The ions are not easily agglomerated, and as can be seen from the tungsten ion backscatter diagram of the SEM in FIG. 1, W is not substantially seen 6+ Ion individual backscattering, with evident W in FIG. 2 6+ Ion backscattering (white area in FIG. 2), illustratingSimple blending, the alumina and tungsten oxide are individually coated, so W 6+ Large particle agglomeration of ions occurs, and obvious W appears in a back scattering diagram 6+ And (3) ion backscattering. So that the alumina can achieve the purpose of improving the conductivity of the coating layer and the electrochemical performance of the material by means of the advantages of tungsten ions.
In summary, the invention provides a coated ternary material and application thereof, wherein the coating layer of the coated ternary material has good electronic conductivity, has good lattice compatibility with the ternary material, and can improve the cycle stability and rate capability of the material.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (10)
1. The coating ternary material is characterized in that a coating layer of the coating ternary material is WAO material, and the WAO material is tungsten oxide doped aluminum oxide; the WAO material is doped with tungsten during the preparation of the alumina, thereby obtaining the WAO material of the alumina doped with tungsten oxide, wherein W 6+ Ion-exchanged portion Al 3+ Ions.
2. The coated ternary material of claim 1, wherein the mass percent of the WAO material is from 0.3wt% to 0.7wt% based on the mass of the coated ternary material.
3. The coated ternary material according to claim 2, wherein the mass ratio of Al element to W element in the WAO material is 1 (2 to 4).
4. The clad ternary material according to claim 1, wherein the content of Al element in the clad ternary material is 500ppm to 1500ppm.
5. The coated ternary material of claim 4, wherein the content of W element in the coated ternary material is 2400ppm to 3200ppm.
6. The coated ternary material of claim 1, wherein the coated ternary material is prepared from a raw material comprising a ternary material-fired product, a WAO material and a solvent.
7. The coated ternary material of claim 6, wherein the solvent comprises ethanol.
8. The clad ternary material of claim 1, wherein the core composition of the clad ternary material comprises LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.55 and less than or equal to 0.60,0.10, and y is more than or equal to 0.12.
9. An electrochemical device comprising the coated ternary material of any one of claims 1 to 8.
10. An electronic device, characterized in that the electronic device comprises the electrochemical apparatus according to claim 9.
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