CN114335500B - SiO2 coated ternary positive electrode material with nano porous structure, and preparation method and application thereof - Google Patents
SiO2 coated ternary positive electrode material with nano porous structure, and preparation method and application thereof Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title 2
- 229910052681 coesite Inorganic materials 0.000 title 1
- 229910052906 cristobalite Inorganic materials 0.000 title 1
- 239000000377 silicon dioxide Substances 0.000 title 1
- 235000012239 silicon dioxide Nutrition 0.000 title 1
- 229910052682 stishovite Inorganic materials 0.000 title 1
- 229910052905 tridymite Inorganic materials 0.000 title 1
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 100
- 238000003756 stirring Methods 0.000 claims description 52
- 239000011159 matrix material Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 32
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 30
- 238000005245 sintering Methods 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 230000007704 transition Effects 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 239000010406 cathode material Substances 0.000 claims description 18
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000010405 anode material Substances 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 239000002245 particle Substances 0.000 description 6
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 2
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
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Abstract
The invention belongs to the technical field of lithium ion battery materials, and discloses a ternary positive electrode material coated by SiO 2 with a nano porous structure and a preparation method thereof.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a ternary positive electrode material coated with SiO 2 with a nano porous structure, and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high voltage, large specific energy, long cycle life, stable working voltage, small self-discharge and the like, and is considered as one of batteries with development potential. The positive electrode material is an important component of the lithium ion battery, and is not only a bottleneck for improving the capacity of the lithium ion battery, but also the most important factor for determining the price of the lithium ion battery. The cathode material with high discharge capacity and stability is sought, and the produced cathode material with excellent and low cost becomes a focus of continuous attention in the industry. The safety, energy density, output performance, circulation and cost of the ternary material are relatively balanced, and the ternary material gradually becomes a development trend of the power battery.
The existing ternary materials also have main technical problems: firstly, the phase transition of the particle surface is easy to cause the attenuation of battery capacity and cycle performance; secondly, particles are broken after circulation, so that electrochemical performance is attenuated, and thermal stability and safety performance are reduced.
In order to improve the stability and electrochemical properties of ternary materials, doping metal ions and non-metal ions into the material lattice or coating the surface of the material with compounds with proper thickness, wherein SiO 2 coating has proven to be an effective measure.
Disclosure of Invention
The invention aims at providing a ternary positive electrode material coated by SiO 2 with a nano porous structure and a preparation method thereof, and the ternary positive electrode material coated by SiO 2 with the nano porous structure, which is obtained by the method, is not only beneficial to the transmission of lithium ions, ensures that the material has higher specific capacity, but also plays a role in isolating electrolyte, and ensures that the material has good cycle performance.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
A preparation method of a ternary positive electrode material coated by SiO 2 with a nano porous structure comprises the following steps:
(1) Preparation of a ternary positive electrode material matrix: mixing the precursor with a lithium source, then sintering at high temperature, and then crushing and grading to obtain a ternary positive electrode material matrix;
(2) Adding the ternary positive electrode material matrix prepared in the step (1) into ethanol solution, uniformly stirring, adding into silicon coating solution, and continuously stirring to obtain a mixture;
(3) Placing the mixture obtained in the step (2) into a water bath kettle, uniformly stirring, placing into a hydrothermal kettle, filling nitrogen into the hydrothermal kettle, heating to a certain temperature and pressure in the hydrothermal kettle, maintaining the temperature and pressure for a period of time, and then decompressing and cooling to obtain transition powder;
(4) Secondary sintering the transition powder obtained in the step (3) in air or oxygen atmosphere, cooling after sintering, and finally crushing, grading and sieving the obtained composite oxide to obtain the ternary anode material coated by SiO 2 with a nano porous structure;
Wherein in the step (1), the precursor is Ni xCoyMn1-x-y(OH)2, x is more than 0, y is more than 0, and 1-x-y is more than 0.
Preferably, in step (1), the lithium source is one or more of lithium nitrate, lithium acetate, lithium carbonate or lithium hydroxide; the molar ratio of the lithium source to the precursor is 1.04-1.08.
Preferably, in the step (2), the preparation method of the silicon coating solution comprises the following steps: adding ethyl orthosilicate into ethanol solution, stirring uniformly, adding a mixture of hydrochloric acid and ethanol into the mixed solution of ethyl orthosilicate and ethanol under stirring, and standing for a period of time to obtain silicon coating liquid.
Preferably, the dosage of the ethyl orthosilicate is 0-2% of the mass of the ternary positive electrode material matrix in the step (1), and the ethyl orthosilicate does not contain 0%.
Preferably, the content of the ethyl orthosilicate is 96%, the mass fraction of the hydrochloric acid is 1%, the purity of the ethanol is 95%, the molar ratio of the hydrochloric acid to the ethyl orthosilicate is 2 x 10 -3, the molar ratio of the ethanol to the ethyl orthosilicate in the mixed solution of the ethyl orthosilicate and the ethanol is 5-8, and the standing time is 30min.
Preferably, the purity of the ethanol in the step (2) is 75%, and the mass ratio of the ternary cathode material matrix to the ethanol is 1-4.
Preferably, in the step (3), the temperature of the water bath kettle is 85 ℃, the stirring time is 60-180 min, the pressure of the pre-filled nitrogen in the hydrothermal kettle is 2MPa, the heating rate of the hydrothermal kettle is 2 ℃/min, the temperature reached after heating is 180-250 ℃, and the pressure is 4MPa.
Preferably, the time of heat preservation and pressure maintaining in the step (3) is 60-180 min, the pressure is released until the pressure in the kettle is reduced to normal pressure, and the pressure release speed is 2 MPa/hour.
In addition, the invention also claims the ternary positive electrode material coated by the SiO 2 with the nano porous structure prepared by the preparation method and the application of the ternary positive electrode material coated by the SiO 2 with the nano porous structure as the positive electrode material of the lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
The invention aims to provide a preparation method of a ternary positive electrode material coated by SiO 2 with a nano porous structure, compared with the existing dry coating method, the method has the advantages that the particle size of the obtained SiO 2 particles is smaller, the particle size distribution is more uniform, the SiO 2 particles can be coated on the surface of the ternary positive electrode material more uniformly, the NCM ternary positive electrode material obtained after the treatment by the method forms a coating layer with the nano porous structure on the surface of the ternary positive electrode material, the nano porous structure is favorable for lithium ion transmission, and the material has higher specific capacity; meanwhile, the SiO 2 nano-particle coating layer also plays a role in isolating electrolyte, so that the material is ensured to have good cycle performance.
Drawings
FIG. 1 is an SEM image of a material prepared according to example 3 of the invention;
FIG. 2 is an SEM image of the material of example 4 of the invention;
FIG. 3 is an SEM image of the material of example 7 of the present invention;
FIG. 4 is an SEM image of SiO 2 prepared according to the present invention;
fig. 5 is a first charge-discharge curve of the material prepared in example 8 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples. Of course, the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Although the steps of the present invention are arranged by reference numerals, the order of the steps is not limited, and the relative order of the steps may be adjusted unless the order of the steps is explicitly stated or the execution of a step requires other steps as a basis. It is to be understood that the term "and/or" as used herein relates to and encompasses any and all possible combinations of one or more of the associated listed items.
Example 1
A preparation method of a ternary positive electrode material coated by SiO 2 with a nano porous structure comprises the following steps:
(1) Preparation of a ternary positive electrode material matrix: mixing a precursor Ni 0.5Co0.2Mn0.3(OH)2 with lithium carbonate, sintering in the air at 910 ℃ for 10 hours, and then crushing and grading to obtain a ternary positive electrode material matrix, wherein the weight of the ternary positive electrode material matrix is 1kg; wherein the molar ratio of lithium carbonate to precursor is 1.05;
(2) Adding 5.00g of ethyl orthosilicate into 5.59g of ethanol solution, uniformly stirring, then adding a mixture of 0.17g of dilute hydrochloric acid and 100.00g of ethanol into the mixed solution of ethyl orthosilicate and ethanol under the stirring condition, and standing for 30min to obtain silicon coating liquid;
(3) Adding 1kg of the ternary cathode material matrix prepared in the step (1) into 250.00g of ethanol solution, rapidly stirring for 10min, adding into the silicon coating solution obtained in the step (2), and continuously stirring for 30min to obtain a mixture;
(4) Placing the mixture obtained in the step (3) into a water bath kettle at 85 ℃, stirring for 60min, placing into a hydrothermal kettle, filling nitrogen into the hydrothermal kettle until the pressure is 2MPa, then heating to 250 ℃ at the rate of 2 ℃/min, heating to 4MPa, performing heat preservation and pressure maintaining for 60min, performing pressure relief to normal pressure, performing pressure relief at the pressure relief speed of 2 MPa/h, and reducing the temperature in the kettle to below 50 ℃ to obtain transition powder;
(5) And (3) sintering the transition powder obtained in the step (4) in air at 600 ℃ for 6 hours, cooling after sintering, and finally crushing, grading and sieving the obtained composite oxide to obtain the ternary anode material coated with SiO 2 with the nano porous structure.
Example 2
A preparation method of a ternary positive electrode material coated by SiO 2 with a nano porous structure comprises the following steps:
(1) Preparation of a ternary positive electrode material matrix: mixing a precursor Ni 0.5Co0.2Mn0.3(OH)2 with lithium carbonate, sintering in air at 950 ℃ for 12 hours, and then crushing and grading to obtain a ternary positive electrode material matrix, wherein the weight of the ternary positive electrode material matrix is 1kg; wherein the molar ratio of lithium carbonate to precursor is 1.06;
(2) Adding 10g of ethyl orthosilicate into 13.41g of ethanol solution, uniformly stirring, then adding a mixture of 0.34g of dilute hydrochloric acid and 100.00g of ethanol into the mixed solution of ethyl orthosilicate and ethanol under the stirring condition, and standing for 30min to obtain silicon coating liquid;
(3) Adding 1kg of the ternary cathode material matrix prepared in the step (1) into 333.33g of ethanol solution, rapidly stirring for 10min, adding into the silicon coating solution obtained in the step (2), and continuously stirring for 30min to obtain a mixture;
(4) Placing the mixture obtained in the step (3) into a water bath kettle at 85 ℃, stirring for 120min, placing into a hydrothermal kettle, filling nitrogen into the hydrothermal kettle until the pressure is 2MPa, then heating to 220 ℃ at a speed of 2 ℃/min, heating to 4MPa, performing heat preservation and pressure maintaining for 120min, performing pressure relief to normal pressure, performing pressure relief at a pressure relief speed of 2 MPa/h, and reducing the temperature in the kettle to below 50 ℃ to obtain transition powder;
(5) And (3) sintering the transition powder obtained in the step (4) in air at 600 ℃ for 6 hours, cooling after sintering, and finally crushing, grading and sieving the obtained composite oxide to obtain the ternary anode material coated with SiO 2 with the nano porous structure.
Example 3
A preparation method of a ternary positive electrode material coated by SiO 2 with a nano porous structure comprises the following steps:
(1) Preparation of a ternary positive electrode material matrix: mixing a precursor Ni 0.6Co0.2Mn0.2(OH)2 with lithium carbonate, sintering in air at 865 ℃ for 10 hours, and then crushing and grading to obtain a ternary positive electrode material matrix, wherein the weight of the ternary positive electrode material matrix is 1kg; wherein the molar ratio of lithium carbonate to precursor is 1.05;
(2) Adding 15.00g of ethyl orthosilicate into 23.46g of ethanol solution, uniformly stirring, then adding a mixture of 0.5g of dilute hydrochloric acid and 100.00g of ethanol into the mixed solution of ethyl orthosilicate and ethanol under the stirring condition, and standing for 30min to obtain silicon coating liquid;
(3) Adding 1kg of the ternary cathode material matrix prepared in the step (1) into 500.00g of ethanol solution, rapidly stirring for 10min, adding into the silicon coating solution obtained in the step (2), and continuously stirring for 30min to obtain a mixture;
(4) Placing the mixture obtained in the step (3) into a water bath kettle at 85 ℃, stirring for 180min, placing into a hydrothermal kettle, filling nitrogen into the hydrothermal kettle until the pressure is 2MPa, then heating to 180 ℃ at a speed of 2 ℃/min, heating to 4MPa, performing heat preservation and pressure maintaining for 180min, performing pressure relief to normal pressure, performing pressure relief at a pressure relief speed of 2 MPa/h, and reducing the temperature in the kettle to below 50 ℃ to obtain transition powder;
(5) And (3) sintering the transition powder obtained in the step (4) in air at 600 ℃ for 6 hours, cooling after sintering, and finally crushing, grading and sieving the obtained composite oxide to obtain the ternary anode material coated with SiO 2 with the nano porous structure.
Example 4
A preparation method of a ternary positive electrode material coated by SiO 2 with a nano porous structure comprises the following steps:
(1) Preparation of a ternary positive electrode material matrix: mixing a precursor Ni 0.6Co0.2Mn0.2(OH)2 with lithium carbonate, sintering in air at 920 ℃ for 12 hours, and then crushing and grading to obtain a ternary positive electrode material matrix, wherein the weight of the ternary positive electrode material matrix is 1kg; wherein the molar ratio of lithium carbonate to precursor is 1.05;
(2) Adding 20.00g of ethyl orthosilicate into 35.75g of ethanol solution, uniformly stirring, then adding a mixture of 0.67g of dilute hydrochloric acid and 100.00g of ethanol into the mixed solution of ethyl orthosilicate and ethanol under the stirring condition, and standing for 30min to obtain silicon coating liquid;
(3) Adding 1kg of the ternary cathode material matrix prepared in the step (1) into 1000.00g of ethanol solution, rapidly stirring for 10min, adding into the silicon coating solution obtained in the step (2), and continuously stirring for 30min to obtain a mixture;
(4) Placing the mixture obtained in the step (3) into a water bath kettle at 85 ℃, stirring for 120min, placing into a hydrothermal kettle, filling nitrogen into the hydrothermal kettle until the pressure is 2MPa, then heating to 200 ℃ at a speed of 2 ℃/min, heating to 4MPa, performing heat preservation and pressure maintaining for 180min, performing pressure relief to normal pressure, performing pressure relief at a pressure relief speed of 2 MPa/h, and reducing the temperature in the kettle to below 50 ℃ to obtain transition powder;
(5) And (3) sintering the transition powder obtained in the step (4) in air at 600 ℃ for 6 hours, cooling after sintering, and finally crushing, grading and sieving the obtained composite oxide to obtain the ternary anode material coated with SiO 2 with the nano porous structure.
Example 5
A preparation method of a ternary positive electrode material coated by SiO 2 with a nano porous structure comprises the following steps:
(1) Preparation of a ternary positive electrode material matrix: mixing a precursor Ni 0.6Co0.2Mn0.2(OH)2 with lithium carbonate, sintering in air at 860 ℃ for 10 hours, and then crushing and grading to obtain a ternary positive electrode material matrix, wherein the weight of the ternary positive electrode material matrix is 1kg; wherein the molar ratio of lithium carbonate to precursor is 1.05;
(2) Adding 5.00g of ethyl orthosilicate into 8.94g of ethanol solution, uniformly stirring, then adding a mixture of 0.17g of dilute hydrochloric acid and 100.00g of ethanol into the mixed solution of ethyl orthosilicate and ethanol under the stirring condition, and standing for 30min to obtain silicon coating liquid;
(3) Adding 1kg of the ternary cathode material matrix prepared in the step (1) into 1000.00g of ethanol solution, rapidly stirring for 10min, adding into the silicon coating solution obtained in the step (2), and continuously stirring for 30min to obtain a mixture;
(4) Placing the mixture obtained in the step (3) into a water bath kettle at 85 ℃, stirring for 180min, placing into a hydrothermal kettle, filling nitrogen into the hydrothermal kettle until the pressure is 2MPa, then heating to 210 ℃ at a speed of 2 ℃/min, heating to 4MPa, maintaining the temperature for 180min, then decompressing to normal pressure, wherein the decompression speed is 2 MPa/h, and reducing the temperature in the kettle to below 50 ℃ to obtain transition powder;
(5) And (3) sintering the transition powder obtained in the step (4) in air at 600 ℃ for 6 hours, cooling after sintering, and finally crushing, grading and sieving the obtained composite oxide to obtain the ternary anode material coated with SiO 2 with the nano porous structure.
Example 6
A preparation method of a ternary positive electrode material coated by SiO 2 with a nano porous structure comprises the following steps:
(1) Preparation of a ternary positive electrode material matrix: mixing a precursor Ni 0.6Co0.2Mn0.2(OH)2 with lithium carbonate, sintering in the air at 910 ℃ for 10 hours, and then crushing and grading to obtain a ternary positive electrode material matrix, wherein the weight of the ternary positive electrode material matrix is 1kg; wherein the molar ratio of lithium carbonate to precursor is 1.05;
(2) Adding 10.00g of ethyl orthosilicate into 15.64g of ethanol solution, uniformly stirring, then adding a mixture of 0.34g of dilute hydrochloric acid and 100.00g of ethanol into the mixed solution of ethyl orthosilicate and ethanol under the stirring condition, and standing for 30min to obtain silicon coating liquid;
(3) Adding 1kg of the ternary cathode material matrix prepared in the step (1) into 500.00g of ethanol solution, rapidly stirring for 10min, adding into the silicon coating solution obtained in the step (2), and continuously stirring for 30min to obtain a mixture;
(4) Placing the mixture obtained in the step (3) into a water bath kettle at 85 ℃, stirring for 120min, placing into a hydrothermal kettle, filling nitrogen into the hydrothermal kettle until the pressure is 2MPa, then heating to 190 ℃ at a speed of 2 ℃/min, heating to 4MPa, performing heat preservation and pressure maintaining for 180min, performing pressure relief to normal pressure, performing pressure relief at a pressure relief speed of 2 MPa/h, and reducing the temperature in the kettle to below 50 ℃ to obtain transition powder;
(5) And (3) sintering the transition powder obtained in the step (4) in air at 600 ℃ for 6 hours, cooling after sintering, and finally crushing, grading and sieving the obtained composite oxide to obtain the ternary anode material coated with SiO 2 with the nano porous structure.
Example 7
A preparation method of a ternary positive electrode material coated by SiO 2 with a nano porous structure comprises the following steps:
(1) Preparation of a ternary positive electrode material matrix: mixing a precursor Ni 0.8Co0.1Mn0.1(OH)2 with lithium hydroxide, sintering in the air at 780 ℃ for 12 hours, and then crushing and grading to obtain a ternary positive electrode material matrix; wherein the molar ratio of lithium hydroxide to precursor is 1.05;
(2) Adding 15.00g of ethyl orthosilicate into 20.11g of ethanol solution, uniformly stirring, then adding a mixture of 0.5g of dilute hydrochloric acid and 100.00g of ethanol into the mixed solution of ethyl orthosilicate and ethanol under the stirring condition, and standing for 30min to obtain silicon coating liquid;
(3) Adding 1kg of the ternary cathode material matrix prepared in the step (1) into 333.33g of ethanol solution, rapidly stirring for 10min, adding into the silicon coating solution obtained in the step (2), and continuously stirring for 30min to obtain a mixture;
(4) Placing the mixture obtained in the step (3) into a water bath kettle at 85 ℃, stirring for 60min, placing into a hydrothermal kettle, filling nitrogen into the hydrothermal kettle until the pressure is 2MPa, then heating to 230 ℃ at a speed of 2 ℃/min, heating to 4MPa, performing heat preservation and pressure maintaining for 120min, performing pressure relief to normal pressure, performing pressure relief at a pressure relief speed of 2 MPa/h, and reducing the temperature in the kettle to below 50 ℃ to obtain transition powder;
(5) And (3) sintering the transition powder obtained in the step (4) in air at 600 ℃ for 6 hours, cooling after sintering, and finally crushing, grading and sieving the obtained composite oxide to obtain the ternary anode material coated with SiO 2 with the nano porous structure.
Example 8
A preparation method of a ternary positive electrode material coated by SiO 2 with a nano porous structure comprises the following steps:
(1) Preparation of a ternary positive electrode material matrix: mixing a precursor Ni 0.8Co0.1Mn0.1(OH)2 with lithium hydroxide, sintering in the air at 840 ℃ for 15 hours, and then crushing and grading to obtain a ternary positive electrode material matrix; wherein the molar ratio of lithium hydroxide to precursor is 1.05;
(2) Adding 20.00g of ethyl orthosilicate into 22.35g of ethanol solution, uniformly stirring, then adding a mixture of 0.67g of dilute hydrochloric acid and 100.00g of ethanol into the mixed solution of ethyl orthosilicate and ethanol under the stirring condition, and standing for 30min to obtain silicon coating liquid;
(3) Adding 1kg of the ternary cathode material matrix prepared in the step (1) into 250.00g of ethanol solution, rapidly stirring for 10min, adding into the silicon coating solution obtained in the step (2), and continuously stirring for 30min to obtain a mixture;
(4) Placing the mixture obtained in the step (3) into a water bath kettle at 85 ℃, stirring for 120min, placing into a hydrothermal kettle, filling nitrogen into the hydrothermal kettle until the pressure is 2MPa, then heating to 240 ℃ at a speed of 2 ℃/min, heating to 4MPa, performing heat preservation and pressure maintaining for 60min, performing pressure relief to normal pressure, performing pressure relief at a pressure relief speed of 2 MPa/h, and reducing the temperature in the kettle to below 50 ℃ to obtain transition powder;
(5) And (3) sintering the transition powder obtained in the step (4) in air at 600 ℃ for 6 hours, cooling after sintering, and finally crushing, grading and sieving the obtained composite oxide to obtain the ternary anode material coated with SiO 2 with the nano porous structure.
The performance of the ternary cathode materials coated with SiO 2 with nano-porous structure prepared in the above examples 1-8 was evaluated as follows:
The nano porous structure SiO 2 coated ternary positive electrode material prepared in the embodiment is taken as a positive electrode by taking a lithium sheet as a negative electrode, a secondary button cell, the model of which is CR2025, is prepared, and under the voltage of 3.0-4.3V, the test of the first charge and discharge, namely 0.1C charge/0.1C discharge, is carried out for two circles, then the test of the first charge and discharge efficiency, the first discharge capacity of 1C and the retention rate of 100 circles are carried out under the condition of 1C charge/1C discharge, and the test results are shown in Table 1.
The foregoing description is only of preferred embodiments of the invention and is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (9)
1. The preparation method of the ternary positive electrode material coated by the SiO 2 with the nano porous structure is characterized by comprising the following steps of:
(1) Preparation of a ternary positive electrode material matrix: mixing the precursor with a lithium source, then sintering at high temperature, and then crushing and grading to obtain a ternary positive electrode material matrix;
(2) Adding the ternary cathode material matrix prepared in the step (1) into ethanol solution, stirring uniformly, adding into silicon coating liquid, and continuously stirring to obtain a mixture, wherein the preparation method of the silicon coating liquid comprises the following steps: adding ethyl orthosilicate into an ethanol solution, uniformly stirring, then adding a mixture of hydrochloric acid and ethanol into the mixed solution of ethyl orthosilicate and ethanol under the stirring condition, and standing for a period of time to obtain a silicon coating solution;
(3) Placing the mixture obtained in the step (2) into a water bath kettle, uniformly stirring, placing into a hydrothermal kettle, filling nitrogen into the hydrothermal kettle, heating to a certain temperature and pressure in the hydrothermal kettle, maintaining the temperature and pressure for a period of time, and then decompressing and cooling to obtain transition powder;
(4) Secondary sintering the transition powder obtained in the step (3) in air or oxygen atmosphere, cooling after sintering, and finally crushing, grading and sieving the obtained composite oxide to obtain the ternary anode material coated by SiO 2 with a nano porous structure;
Wherein in the step (1), the precursor is Ni xCoyMn1-x-y(OH)2, x is more than 0, y is more than 0, and 1-x-y is more than 0.
2. The method of claim 1, wherein in step (1), the lithium source is one or more of lithium nitrate, lithium acetate, lithium carbonate, or lithium hydroxide; the molar ratio of the lithium source to the precursor is 1.04-1.08.
3. The preparation method according to claim 1, wherein the amount of the ethyl orthosilicate is 0-2% of the mass of the ternary cathode material matrix in the step (1), and is not 0%.
4. The preparation method according to claim 1, wherein the content of the ethyl orthosilicate is 96%, the mass fraction of the hydrochloric acid is 1%, the purity of the ethanol is 95%, the molar ratio of the hydrochloric acid to the ethyl orthosilicate is 2 x 10 -3, the molar ratio of the ethanol to the ethyl orthosilicate in the mixed solution of the ethyl orthosilicate and the ethanol is 5-8, and the standing time is 30min.
5. The method according to claim 1, wherein the purity of ethanol in the step (2) is 75%, and the mass ratio of the ternary cathode material matrix to ethanol is 1 to 4.
6. The preparation method according to claim 1, wherein in the step (3), the temperature of the water bath kettle is 85 ℃, the stirring time is 60-180 min, the pressure of the pre-filled nitrogen in the hydrothermal kettle is 2MPa, the heating rate of the hydrothermal kettle is 2 ℃/min, and the temperature reached after heating is 180-250 ℃ and the pressure is 4MPa.
7. The preparation method according to claim 1, wherein the time of heat preservation and pressure maintaining in the step (3) is 60-180 min, the pressure is released until the pressure in the kettle is reduced to normal pressure, and the pressure release speed is 2 MPa/h.
8. A ternary cathode material coated with SiO 2 having a nanoporous structure prepared by the method of any one of claims 1 to 7.
9. Use of a ternary cathode material coated with a nanoporous structure SiO 2 according to claim 8 as a cathode material for a lithium ion battery.
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