CN114864910A - Coated ternary material and application thereof - Google Patents
Coated ternary material and application thereof Download PDFInfo
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- CN114864910A CN114864910A CN202210672552.1A CN202210672552A CN114864910A CN 114864910 A CN114864910 A CN 114864910A CN 202210672552 A CN202210672552 A CN 202210672552A CN 114864910 A CN114864910 A CN 114864910A
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- 239000000463 material Substances 0.000 title claims abstract description 160
- 239000011247 coating layer Substances 0.000 claims abstract description 32
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 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 13
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 229910013716 LiNi Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 20
- 238000007599 discharging Methods 0.000 description 12
- 229910052721 tungsten Inorganic materials 0.000 description 12
- 239000010937 tungsten Substances 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- -1 tungsten ions Chemical class 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005253 cladding Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 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
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011888 foil 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
- 238000000034 method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002002 slurry Substances 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
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 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
- 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
- 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
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 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
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- H01M4/624—Electric conductive fillers
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention provides a coated ternary material and application thereof. The invention adopts tungsten oxide doped aluminum oxide material WAO as the coating layer of the ternary material, overcomes the problem of poor conductivity of the aluminum oxide coating layer, and combines W 6+ Has the kinetic advantage that the WAO coating layer hasGood ionic conductivity and electronic conductivity, improves the lattice compatibility of the coating layer and the ternary material, and effectively improves the cycle stability and rate capability of the ternary material.
Description
Technical Field
The invention belongs to the technical field of batteries, relates to a ternary material, and particularly relates to a coated ternary material and application thereof.
Background
At present, the working voltage of a commercial ternary material battery is about 4.2-4.35V, the utilization rate of reversible lithium is insufficient, and the charging voltage needs to be increased 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 positive electrode/electrolyte interface performance due to surface side reactions, which is manifested by severe increase in gas generation and significant increase in DCR (direct current internal resistance) during cycling.
The problem can be effectively improved by coating the alumina coating on the surface of the ternary material, and a layer of compact alumina coating is formed on the surface of the coated ternary material, so that the side reaction of an electrode-electrolyte interface can be reduced to the maximum extent, and the impedance is increased during control circulation; however, the coating itself often exhibits poor Li + Conductivity, and inhibition of 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 electronic conductivity and good lattice compatibility with the ternary material, and can improve the cycling stability and rate capability of the material.
Disclosure of Invention
The invention aims to provide a coated ternary material and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a coated ternary material, wherein a coating layer of the coated ternary material comprises a WAO material, and the WAO material is tungsten oxide doped aluminum oxide.
The invention adopts tungsten oxide doped aluminum oxide material WAO as the coating layer of the ternary material, overcomes the problem of poor conductivity of the aluminum oxide coating layer, and combines W 6+ The dynamic advantage of the composite material enables the WAO coating layer to have good ionic conductivity and electronic conductivity, improves the lattice compatibility of the coating layer and the ternary material, and effectively improves the cycle stability and the rate capability of the ternary material; wherein, in the WAO material, W 6+ Ion replacement of part of Al 3+ Ions, W in WAO materials compared to simply mixed tungsten oxide and aluminum oxide materials 6+ Ions are uniformly distributed in the alumina crystal lattice, so that the alumina can achieve the purpose of improving the conductivity of the coating layer by virtue of the advantages of tungsten ions.
W in the WAO material of the invention represents tungsten element, and A represents aluminum element.
Preferably, the mass percent of the WAO material is 0.3 wt% to 0.7 wt%, based on the mass of the clad ternary material, and may be, for example, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.55 wt%, 0.6 wt%, 0.65 wt%, or 0.7 wt%, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
The WAO material disclosed by the invention can simultaneously ensure that the ternary material has high energy density and simultaneously has good conductivity and dynamic performance within a reasonable coating amount range.
Preferably, the WAO material has a mass ratio of Al element to W element of 1 (2 to 4), such as 1:2, 1:2.5, 1:3, 1:3.5 or 1:4, but not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the Al element content in the clad ternary material is 500ppm to 1500ppm, and may be, for example, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm, 1000ppm, 1100ppm, 1200ppm, 1300ppm, 1400ppm or 1500ppm, but is not limited to the recited values, and other values not recited in the numerical ranges are also applicable.
Preferably, the amount of W element in the coated ternary material is 2400ppm to 3200ppm, and may be 2400ppm, 2500ppm, 2600ppm, 2700ppm, 2800ppm, 2900ppm, 3000ppm, 3100ppm or 3200ppm, for example, but not limited to the recited values, and other values not recited in the numerical ranges are also applicable.
The invention can obtain a thin and uniform WAO coating layer on the surface of the ternary material particles by controlling the amount and the element ratio of two oxides in the WAO material.
Preferably, the raw materials for preparing the coated ternary material comprise ternary material calcined product, WAO material and solvent.
Preferably, the solvent comprises ethanol.
According to the invention, a primary burned product of a ternary material is mixed with a WAO material, and the WAO material is uniformly coated on the surface of the ternary material by wet coating and using ethanol as a solvent; in addition, the wet coating is stirred in the solvent until the solvent is completely volatilized, and compared with the dry coating, the coating can be more uniform.
The invention adopts volatile ethanol as the solvent, can avoid the ternary material and the WAO material from being damaged, and can avoid the influence of the residual solvent on the performance of the coated ternary material.
Preferably, the core body composition of the coated 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, and y is more than or equal to 0.10 and less than or equal to 0.12.
The core body composition of the coated ternary material provided by the invention can give consideration to low cost, high safety and high performance.
The core body composition of the coated ternary material comprises LiNi x Co y Mn 1-x-y O 2 Where 0.55. ltoreq. x.ltoreq.0.60, for example 0.55, 0.56, 0.57, 0.58, 0.59 or 0.60, but is not limited to the values listed, other values not listed in the numerical rangeThe same applies.
The core body composition of the coated ternary material comprises LiNi x Co y Mn 1-x-y O 2 Where 0.10. ltoreq. y.ltoreq.0.12, for example 0.1, 0.105, 0.11, 0.115 or 0.12, but is not limited to the values listed, and other values not listed in the numerical range are likewise suitable.
The preparation method of the coated ternary material comprises the following steps:
and mixing the ternary material calcined product, the WAO material and the solvent, stirring to completely volatilize the solvent, and sintering the obtained mixture to obtain the coated ternary material.
Preferably, the particle size of the WAO material is on the nanometer scale.
Preferably, the solvent is ethanol.
Preferably, the sintering temperature is from 300 ℃ to 600 ℃, for example, it may be 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃, but is not limited to the recited values, and other values not recited within the numerical range are equally applicable.
Preferably, the sintering time is 10h to 18h, for example 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h or 18h, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
In a second aspect, the present invention provides an electrochemical device comprising the encapsulated ternary material according to the first aspect.
Preferably, the positive electrode sheet of the electrochemical device includes the doped ternary material, the conductive agent and the polyvinylidene fluoride in a mass ratio of (90 to 99): 0.1 to 7):1, for example, 90:0.1:1, 92:1:1, 94:5:1 or 99:7:1, but not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
Preferably, the positive electrode current collector of the electrochemical device is an aluminum foil.
Preferably, the negative electrode sheet of the electrochemical device includes graphite, conductive carbon black, sodium carboxymethylcellulose, and styrene butadiene rubber in a mass ratio of (90 to 99): 0.1 to 2): 0.5 to 3):2, which 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 is not limited to the enumerated values, and other unrecited values within the numerical range 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 according to 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 pure alumina coating layer is solved by means of tungsten ions in the WAO material, so that the coating layer has good ionic conductivity and electronic conductivity, the lattice compatibility of the coating layer and the ternary material is improved, and the circulation stability and the rate capability of the ternary material are effectively improved; in addition, the invention adopts wet coating, a calcined product of ternary materials is used for coating in the coating process, and the solvent is completely volatilized by stirring and then is sintered, so that a uniform coating layer can be obtained.
Drawings
FIG. 1 is a back-scattering diagram of a tungsten ion in an SEM of a cladding type ternary material according to embodiment 1 of the invention;
FIG. 2 is a diagram of a back-scattering pattern of tungsten ions from an SEM of a coated ternary material according to comparative example 3 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a coated ternary material, and the core body of the coated ternary material is composed of LiNi 0.58 Co 0.11 Mn 0.31 O 2 The coating layer is made of WAO material, and the WAO material is tungsten oxide doped aluminum oxide;
based on the mass of the cladding type ternary material, the mass percent of the WAO material is 0.54 wt%, the content of the Al element is 1000ppm, and the content of the W element is 2800 ppm;
in the WAO material, the mass ratio of Al element to W element is 1: 3;
the preparation raw materials of the coated ternary material comprise a ternary material calcined product, a WAO material and ethanol;
the preparation method of the coated ternary material comprises the following steps:
mixing the ternary material calcined product, the WAO material and ethanol, stirring to completely volatilize the ethanol, and sintering the obtained mixture at 450 ℃ for 15h to obtain the coated ternary material, wherein a tungsten ion backscattering diagram of SEM is shown in figure 1;
and doping tungsten in the WAO material in the preparation process of the aluminum oxide, thereby obtaining the WAO material of the tungsten oxide doped aluminum oxide.
Example 2
This example provides a coated ternary material having a core body composition comprising LiNi 0.6 Co 0.12 Mn 0.28 O 2 The coating layer is made of WAO material, and the WAO material is tungsten oxide doped aluminum oxide;
based on the mass of the cladding type ternary material, the mass percent of the WAO material is 0.3 wt%, the content of the Al element is 700ppm, and the content of the W element is 1400 ppm;
in the WAO material, the mass ratio of Al element to W element is 1: 2;
the preparation raw materials of the coated ternary material comprise a ternary material calcined product, a WAO material and ethanol;
the preparation method of the coated ternary material comprises the following steps:
mixing the ternary material calcined product, the WAO material and ethanol, stirring to completely volatilize the ethanol, and sintering the obtained mixture at 300 ℃ for 18h to obtain the coated ternary material;
and doping tungsten in the WAO material in the preparation process of the aluminum oxide, thereby obtaining the WAO material of the tungsten oxide doped aluminum oxide.
Example 3
This example provides a coated ternary material having a core body composition comprising LiNi 0.58 Co 0.11 Mn 0.31 O 2 The coating layer is made of WAO material, and the WAO material is tungsten oxide doped aluminum oxide;
based on the mass of the cladding type ternary material, the mass percent of the WAO material is 0.7 wt%, the content of the Al element is 1000ppm, and the content of the W element is 4000 ppm;
in the WAO material, the mass ratio of Al element to W element is 1: 4;
the preparation raw materials of the coated ternary material comprise a ternary material calcined product, a WAO material and ethanol;
the preparation method of the coated ternary material comprises the following steps:
mixing the ternary material calcined product, the WAO material and ethanol, stirring to completely volatilize the ethanol, and sintering the obtained mixture at 600 ℃ for 10 hours to obtain the coated ternary material;
and doping tungsten in the WAO material in the preparation process of the aluminum oxide, thereby obtaining the WAO material of the tungsten oxide doped aluminum oxide.
Examples 4 and 5 provide clad ternary materials as shown in table 2, which are the same as those of example 1 except that the content of Al element is changed.
Examples 6 and 7 provide coated ternary materials as shown in Table 3, which are the same as those of example 1 except that the content of the W element is changed.
Examples 8 and 9 provide clad ternary materials as shown in table 4, which are the same as example 1 except for the change in mass percent of the WAO material.
The coated ternary material provided in example 10 is as shown in table 5, except that the raw materials for preparing the coated ternary material only include ternary material calcined product and WAO material, and the coating is performed by dry method through simple mixing, the rest is the same as example 1.
Comparative example 1 provides a ternary material having the same composition as the core body described in example 1, and not including a coating.
The ternary material provided in comparative example 2 is the same as example 1 except that the coating layer of the ternary material is a simple alumina coating layer, as shown in table 6.
The ternary material provided in comparative example 3 is as shown in table 6, and the same as example 1 except that the coating layer of the ternary material is a mixed coating layer of alumina and an oxide; the backscattering pattern of tungsten ions for the SEM of the ternary material described in this comparative example is shown in figure 2.
Mixing the coated ternary material obtained in the embodiment and the ternary material obtained in the comparative example with conductive carbon black, a carbon nano tube and polyvinylidene fluoride according to the mass ratio of 97:1:0.5:1, placing the mixture in an N-methyl pyrrolidone solvent to prepare slurry, coating the slurry on an aluminum foil, drying and rolling the aluminum foil to obtain a positive plate; putting graphite, conductive carbon black, sodium carboxymethylcellulose and styrene butadiene rubber in a mass ratio of 96:0.5:0.5:2 into an N-methyl pyrrolidone solvent, coating the obtained slurry on a copper foil, drying and rolling to obtain a negative plate; and assembling the obtained positive plate, the polyethylene diaphragm and the lithium hexafluorophosphate electrolyte into the lithium ion battery.
According to the invention, the elements and contents of the coated ternary material can be obtained by testing the powder obtained by scraping the powder from the anode plate obtained by disassembling the lithium ion battery by using an inductively coupled plasma method.
Gram volume test method: under the condition of 25 ℃, charging and discharging for one week in a charging and discharging mode of 0.063A/g, wherein the cut-off voltage is 2.8-4.4V, and the obtained charging/discharging capacity is divided by the usage amount of the positive electrode, namely the first charging/discharging gram capacity; the test equipment is a battery performance test system (equipment model: BTS05/10C8D-HP) of the Shenghong electric appliance GmbH.
Circulation capacity retention test method: the obtained lithium ion battery is cycled at 25 ℃ in a charging and discharging mode of 0.19A/g (calculated by the mass of the anode material), and after the cycle is up to 800 weeks, the discharge capacity of the battery at the moment is divided by the discharge capacity of the first cycle, so that the cycle capacity retention rate of the battery at 800 cycles is obtained; the test equipment is a battery performance test system (equipment model: BTS05/10C8D-HP) of the Shenghong electric appliance GmbH.
The method for testing the rate capacity retention rate comprises the following steps: at 25 ℃, charging and discharging for three weeks in a charging and discharging mode of 0.063A/g (0.33C), wherein the cut-off voltage is 2.8-4.4V, and the discharge capacity in the third week is recorded; then charging and discharging for one week in a charging and discharging mode of 0.57A/g (3C), recording the discharging capacity and dividing the discharging capacity by the discharging capacity at 0.33C to obtain the high-rate capacity retention rate of the battery; the test equipment is a battery performance test system (equipment model: BTS05/10C8D-HP) of the Shenghong electric appliance GmbH.
The test results are shown in the following table:
TABLE 1
3C rate capacity retention (%) | Retention ratio of 800-week-cycle Capacity (%) | |
Example 1 | 70 | 95 |
Example 2 | 63 | 92 |
Example 3 | 65 | 93 |
TABLE 2
TABLE 3
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 WAO material is used as the coating layer, so that the conductivity of the coating layer can be improved, and the rate capability and the cycle performance of the battery can be improved; from examples 1 and 4 to 9, it is understood that the contents of Al element, W element and the coating material are in reasonable ranges, and the obtained coating layer can be thin and uniform, thereby obtaining a ternary material having excellent overall performance; as can be seen from examples 1 and 10, the present invention adopts wet coating, and volatile ethanol is used as a coating solvent, so that the distribution of the coating material is more uniform compared with dry coating, thereby improving the comprehensive properties of the material.
(2) As can be seen from example 1 and comparative example 1, the WAO coating layer of the present invention can be improvedThe rate and cycle performance of the battery; as can be seen from the examples 1 and the comparative examples 2, the coating layer of the present invention can overcome the defect of using the single-purity alumina as the coating layer; as can be seen from examples 1 and 3, in comparative example 3, in which a mixture of alumina and tungsten oxide is used as a clad layer, unlike the WAO clad layer of the present invention, W in the WAO material of the present invention 6+ Ions are uniformly distributed in alumina crystal lattices, the dispersibility is good, and W 6+ The ions were not easily agglomerated, and as can be seen from the tungsten ion back-scattering pattern of the SEM in FIG. 1, W was not substantially observed 6+ Back-scattering of the ions alone, with a significant W in FIG. 2 6+ Ion backscattering (white area in FIG. 2), illustrating simple blending, alumina and tungsten oxide are each separately coated, so W 6+ The ions can be agglomerated into large particles, and the back scattering image shows obvious W 6+ The ions are back-scattered. Therefore, the aluminum oxide can achieve the purposes of improving the conductivity of the cladding layer and the electrochemical performance of the material by virtue of the advantages of tungsten ions.
In conclusion, the invention provides a coated ternary material and application thereof, wherein a coating layer of the coated ternary material has good electronic conductivity and good lattice compatibility with the ternary material, and the cycling stability and rate capability of the material can be improved.
The above description is only for the specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. The coated ternary material is characterized in that a coating layer of the coated ternary material comprises a WAO material, and the WAO material is tungsten oxide doped aluminum oxide.
2. The clad ternary material of claim 1 wherein the mass percent of the WAO material is 0.3 wt% to 0.7 wt% based on the mass of the clad ternary material.
3. The clad ternary material according to claim 2, wherein the mass ratio of the Al element to the W element in the WAO material is 1 (2 to 4).
4. The clad ternary material as claimed in claim 1, wherein the content of Al element in the clad ternary material is 500ppm to 1500 ppm.
5. The clad ternary material as claimed in claim 4, wherein the content of W element in the clad ternary material is 2400ppm to 3200 ppm.
6. The coated ternary material as claimed in claim 1, wherein the raw materials for preparing the coated ternary material comprise ternary material calcined product, WAO material and solvent.
7. The encapsulated ternary material of claim 6 wherein said solvent comprises ethanol.
8. The coated ternary material of claim 1 wherein the core composition of the coated 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, and y is more than or equal to 0.10 and less than or equal to 0.12.
9. An electrochemical device comprising the encapsulated ternary material of any one of claims 1 to 8.
10. An electronic device, characterized in that the electronic device comprises the electrochemical device according to claim 9.
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