CN113871611A - High-entropy oxide material composite ternary material and preparation method thereof - Google Patents
High-entropy oxide material composite ternary material and preparation method thereof Download PDFInfo
- Publication number
- CN113871611A CN113871611A CN202110965375.1A CN202110965375A CN113871611A CN 113871611 A CN113871611 A CN 113871611A CN 202110965375 A CN202110965375 A CN 202110965375A CN 113871611 A CN113871611 A CN 113871611A
- Authority
- CN
- China
- Prior art keywords
- entropy oxide
- ternary material
- preparation
- entropy
- dry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 150000002823 nitrates Chemical class 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 18
- 239000011888 foil Substances 0.000 description 18
- 238000002156 mixing Methods 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 239000002033 PVDF binder Substances 0.000 description 12
- 239000006230 acetylene black Substances 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 239000010405 anode material Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 239000013543 active substance Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 238000004080 punching Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000005341 toughened glass Substances 0.000 description 6
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
Images
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
- H01M4/48—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
- H01M4/36—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
-
- 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 belongs to the technical field of lithium ion battery materials, and discloses a high-entropy oxide material composite ternary material and a preparation method thereof, wherein nitrates of five elements of Co, Fe, Cu, Mg, Ni, Zn and Al are dissolved in water according to a certain molar ratio and stirred to dry, and then the high-entropy oxide is obtained by high-temperature (1000 ℃) calcination. And uniformly dispersing the ternary material in an ethanol solution, adding the high-entropy oxide into the solution, stirring to dry, and calcining at low temperature to obtain the ternary material coated with the high-entropy oxide. According to the invention, the ternary material is coated and modified by preparing the high-entropy oxide, so that the ionic conductivity and the structural stability of the material are improved, the storage performance of the material is also improved, and the method has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery manufacturing, and particularly relates to a high-entropy oxide material composite ternary material and a preparation method thereof.
Background
The lithium ion battery as a novel energy storage device has the advantages of high energy density, excellent cycle performance, environmental protection, safety, no memory effect and the like, and is widely applied to various fields. In order to meet the demand of social development, lithium ion batteries are developing toward high specific energy and high power, which requires high stability and high capacity retention of electrode materials.
The ternary material is currently the most promising positive electrode material of lithium ion batteries, and most of the ternary materials researched mainly comprise nickel cobalt lithium manganate (NCM622, NCM811) and nickel cobalt lithium aluminate (NCA 811). Ternary materials incorporating LiCoO2And LiNiO2Has the advantages that: LiCoO2Good cycle performance and LiNiO2The lithium ion battery anode material has high specific capacity and is most hopeful to be widely applied. However, ternary materials also present a number of problems: although the capacity of the battery is increased along with the increase of the content of nickel, the cycle performance of the battery is also deteriorated, and the ternary material is easy to react with CO in the air2And H2The O reacts and causes severe gas expansion, which results in reduced cycle performance.
Aiming at the problem of poor stability of ternary materials, the existing modification method mainly comprises element doping, surface coating and process optimization. The surface coating can form a protective layer on the surface of the ternary material, so that the direct contact between the material and the electrolyte is avoided, and the occurrence of side reactions is reduced. The high-entropy oxide has good ionic conductivity, can effectively improve the lithium ion transmission rate of the material, and further improves the rate capability of the material. Meanwhile, the high-entropy oxide serving as a coating can protect the surface of the ternary material and isolate the occurrence of side reactions between the surface of the electrode and electrolyte.
Disclosure of Invention
In order to solve the problems of the ternary material, the invention mainly aims to provide a high-entropy oxide material composite ternary material and a preparation method thereof. The invention aims to synthesize the high-entropy oxide material with high ionic conductivity, so that the ionic conductivity of the ternary material can be improved, and the stability of the battery can be further improved.
The purpose of the invention is realized by the following technical scheme:
a high-entropy oxide material composite ternary material and a preparation method thereof comprise the following steps:
(1) nitrate of five elements of Co, Fe, Cu, Mg, Ni, Zn and Al is dissolved in water according to a certain molar ratio and stirred to dry, and then the high-entropy oxide is obtained after high-temperature calcination for a certain time.
(2) Uniformly dispersing the ternary material in a solvent A, adding the high-entropy oxide prepared in the step (1) into the solution, stirring to dry, and calcining at low temperature for a certain time to obtain the ternary material coated by the high-entropy oxide.
The mole ratio of the five nitrates in the step (1) is 1:1:1:1: 1.
The stirring-drying temperature in the step (1) is 80-100 ℃, and preferably 85 ℃.
The calcination temperature in the step (1) is 1000-1500 ℃, preferably 1150 ℃. The calcination time is 0.5 to 10 hours, preferably 2 hours.
The calcining atmosphere in the step (1) is one of air or oxygen atmosphere.
In the step (2), the solvent A is one or more of ethanol, glycol and acetone, and ethanol is preferred.
The mass ratio of the high-entropy oxide to the ternary material in the step (2) is 0.1-10%, preferably 5%.
The calcination temperature in the step (2) is 500-600 ℃, preferably 500 ℃. The calcination time is 0.5-5h, preferably 1 h.
According to the invention, the high-entropy oxide is synthesized by a simple solid-phase method, and is further compounded with the ternary cathode material, and finally, a layer of high-entropy oxide material is uniformly coated on the surface of the ternary cathode material on the premise of not damaging the structure of the cathode material as much as possible, so that the conductivity and the stability of the cathode material are improved.
Drawings
FIG. 1 shows the cycle performance of the product of example 1 of the present invention.
Detailed Description
Example 1
(1) Mixing Co (NO)3)2、Fe(NO3)2、Cu(NO3)2、Mg(NO3)2、Ni(NO3)2Dissolving in water at a molar ratio of 1:1:1:1:1, stirring, and air-drying at 1150 deg.CAfter calcining for 2h, the high-entropy oxide is obtained.
(2) 5g of ternary material LiNi0.5Co0.2Mn0.3O2Uniformly dispersing in ethanol, adding 0.25g of the high-entropy oxide prepared in the step (1) into the solution, stirring to dry, and calcining at 500 ℃ for 1h in an oxygen atmosphere to obtain the high-entropy oxide-coated ternary material.
With modified LiNi0.5Co0.2Mn0.3O2The method comprises the following steps of taking positive electrode material powder as an active substance, mixing the active substance with conductive agent Acetylene Black (AB) and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, placing the mixture in a small beaker, and stirring and mixing the mixture for 2 hours at a rotating speed of 800r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h at 105 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content both lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and then assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
As shown in fig. 1, after the battery assembly was aged for 12 hours, charge and discharge tests at different potentials were performed. The sample was activated at 4.5V for 3 cycles at 0.1C and then cycled at 5C rate for 100 cycles. The specific discharge capacity after 100 cycles is 106.3mA h g-1The capacity retention rate was 78.5%.
Example 2
(1) Mixing Co (NO)3)2、Fe(NO3)2、Cu(NO3)2、Mg(NO3)2、Ni(NO3)2Dissolving the mixture in water according to the mol ratio of 1:1:1:1:1, stirring the mixture to dry, and then calcining the mixture in air at 1150 ℃ for 2 hours to obtain the high-entropy oxide.
(2) 5g of ternary material LiNi0.5Co0.2Mn0.3O2Uniformly dispersing in ethanol, and collectingAnd (2) adding 0.1g of the high-entropy oxide prepared in the step (1) into the solution, stirring to dry, and calcining for 1h at 500 ℃ in an oxygen atmosphere to obtain the high-entropy oxide-coated ternary material.
Taking modified anode material powder as an active substance, mixing the modified anode material powder with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to a mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, placing the mixture in a small beaker, and stirring and mixing the mixture for 2 hours at a rotating speed of 1000r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h in the vacuum drying oven at 100 ℃, placing the pole piece in a glove box with the water content and the oxygen content of less than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and then assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The sample was activated at 4.5V for 3 cycles at 0.1C and then cycled at 5C rate for 100 cycles. The specific discharge capacity after 100 cycles is 93.5mA h g-1The capacity retention rate was 70.2%.
Example 3
(1) Mixing Co (NO)3)2、Fe(NO3)2、Cu(NO3)2、Zn(NO3)2、Ni(NO3)2Dissolving the mixture in water according to the mol ratio of 1:1:1:1:1, stirring the mixture to dry, and then calcining the mixture in air at 1150 ℃ for 2 hours to obtain the high-entropy oxide.
(2) 5g of ternary material LiNi0.5Co0.2Mn0.3O2Uniformly dispersing in ethanol, adding 0.25g of the high-entropy oxide prepared in the step (1) into the solution, stirring to dry, and calcining at 500 ℃ for 1h in an oxygen atmosphere to obtain the high-entropy oxide-coated ternary material.
Taking modified anode material powder as an active substance, mixing the modified anode material powder with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to a mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, placing the mixture in a small beaker, and stirring and mixing the mixture for 2 hours at a rotating speed of 1000r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h in the vacuum drying oven at 100 ℃, placing the pole piece in a glove box with the water content and the oxygen content of less than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and then assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The sample was activated at 4.5V for 3 cycles at 0.1C and then cycled at 5C rate for 100 cycles. The specific discharge capacity after 100 cycles is 113.1mA h g-1The capacity retention rate was 84.6%.
Example 4
(1) Mixing Co (NO)3)2、Fe(NO3)2、Al(NO3)3、Zn(NO3)2、Ni(NO3)2Dissolving the mixture in water according to the mol ratio of 1:1:1:1:1, stirring the mixture to dry, and then calcining the mixture in air at 1150 ℃ for 2 hours to obtain the high-entropy oxide.
(2) 5g of ternary material LiNi0.5Co0.2Mn0.3O2Uniformly dispersing in ethanol, adding 0.25g of the high-entropy oxide prepared in the step (1) into the solution, stirring to dry, and calcining at 500 ℃ for 1h in an oxygen atmosphere to obtain the high-entropy oxide-coated ternary material.
Taking modified anode material powder as an active substance, mixing the modified anode material powder with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to a mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, placing the mixture in a small beaker, and stirring and mixing the mixture for 2 hours at a rotating speed of 1000r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h in the vacuum drying oven at 100 ℃, placing the pole piece in a glove box with the water content and the oxygen content of less than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and then assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The sample was activated at 4.5V for 3 cycles at 0.1C and then cycled at 5C rate for 100 cycles. The specific discharge capacity after 100 cycles is 120.5mA h g-1The capacity retention rate was 86%.
Example 5
(1) Mixing Co (NO)3)2、Fe(NO3)2、Al(NO3)3、Zn(NO3)2、Ni(NO3)2Dissolving the mixture in water according to the mol ratio of 1:1:1:1:1, stirring the mixture to dry, and then calcining the mixture in air at 1150 ℃ for 2 hours to obtain the high-entropy oxide.
(2) 5g of ternary material LiNi0.8Co0.1Mn0.1O2Uniformly dispersing in ethanol, adding 0.25g of the high-entropy oxide prepared in the step (1) into the solution, stirring to dry, and calcining at 500 ℃ for 1h in an oxygen atmosphere to obtain the high-entropy oxide-coated ternary material.
Taking modified anode material powder as an active substance, mixing the modified anode material powder with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to a mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, placing the mixture in a small beaker, and stirring and mixing the mixture for 2 hours at a rotating speed of 1000r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h at 95 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content both lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and then assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The sample was activated at 4.5V for 3 cycles at 0.1C and then cycled at 5C rate for 100 cycles. The specific discharge capacity after 100 cycles is 131.4mA h g-1The capacity retention rate was 88.5%.
Example 6
(1) Mixing Co (NO)3)2、Fe(NO3)2、Al(NO3)3、Zn(NO3)2、Ni(NO3)2Dissolving the mixture in water according to the mol ratio of 1:1:1:1:1, stirring the mixture to dry, and then calcining the mixture in air at 1150 ℃ for 2 hours to obtain the high-entropy oxide.
(2) 5g of ternary material LiNi0.6Co0.2Mn0.2O2Uniformly dispersing in ethanol, adding 0.25g of the high-entropy oxide prepared in the step (1) into the solution, stirring to dry, and calcining at 500 ℃ for 1h in an oxygen atmosphere to obtain the high-entropy oxide-coated ternary material.
Taking modified anode material powder as an active substance, mixing the modified anode material powder with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to a mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, placing the mixture in a small beaker, and stirring and mixing the mixture for 2 hours at a rotating speed of 1000r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h at 95 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content both lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and then assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
After the battery is assembled and aged for 12 hours, charging at different potentials is carried outAnd (5) discharging and testing. The sample was activated at 4.5V for 3 cycles at 0.1C and then cycled at 5C rate for 100 cycles. The specific discharge capacity after 100 cycles is 123.5mA h g-1The capacity retention rate was 89.3%.
The above description is only a basic description of the present invention, and any equivalent changes made according to the technical solution of the present invention should fall within the protection scope of the present invention.
Claims (10)
1. A high-entropy oxide material composite ternary material and a preparation method thereof are characterized by comprising the following steps:
(1) nitrate of five elements of Co, Fe, Cu, Mg, Ni, Zn and Al is dissolved in water according to a certain molar ratio and stirred to dry, and then the high-entropy oxide is obtained after high-temperature calcination for a certain time.
(2) Uniformly dispersing the ternary material in a solvent A, adding the high-entropy oxide prepared in the step (1) into the solution, stirring to dry, and calcining at low temperature for a certain time to obtain the ternary material coated by the high-entropy oxide.
2. A high-entropy oxide material composite ternary material and a preparation method thereof according to claim 1, characterized in that the mole ratio of the five nitrates in the step (1) is 1:1:1:1: 1.
3. A high entropy oxide material composite ternary material and its preparation method according to claim 1, characterized in that, the temperature of stirring dry in step (1) is 80-100 ℃.
4. The high-entropy oxide material composite ternary material and the preparation method thereof as claimed in claim 1, wherein the calcination temperature in step (1) is 1000-1500 ℃.
5. A high entropy oxide material composite ternary material and its preparation method according to claim 1, characterized in that, the calcination time in step (1) is 0.5-10 h.
6. A high entropy oxide material composite ternary material and its preparation method according to claim 1, characterized in that, the calcination atmosphere in step (1) is air or oxygen atmosphere.
7. A high-entropy oxide material composite ternary material and a preparation method thereof according to claim 1, wherein the solvent A in the step (2) is one or more of ethanol, ethylene glycol and acetone.
8. A high entropy oxide material composite ternary material and a preparation method thereof according to claim 1, characterized in that, the mass ratio of the high entropy oxide and the ternary material in the step (2) is 0.1% -10%.
9. The high-entropy oxide material composite ternary material and the preparation method thereof as claimed in claim 1, wherein the calcination temperature in the step (2) is 500-600 ℃.
10. A high entropy oxide material composite ternary material and its preparation method according to claim 1, characterized in that, the calcination time in step (2) is 0.5-5 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110965375.1A CN113871611B (en) | 2021-08-23 | 2021-08-23 | Preparation method of high-entropy oxide material composite ternary material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110965375.1A CN113871611B (en) | 2021-08-23 | 2021-08-23 | Preparation method of high-entropy oxide material composite ternary material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113871611A true CN113871611A (en) | 2021-12-31 |
| CN113871611B CN113871611B (en) | 2023-12-05 |
Family
ID=78988192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110965375.1A Active CN113871611B (en) | 2021-08-23 | 2021-08-23 | Preparation method of high-entropy oxide material composite ternary material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113871611B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114883522A (en) * | 2022-04-20 | 2022-08-09 | 南京邮电大学 | High-entropy-like multi-element layered transition metal oxide cathode material and preparation method and application thereof |
| CN115050940A (en) * | 2022-06-21 | 2022-09-13 | 北京理工大学重庆创新中心 | High-entropy ceramic modified cathode material and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101425576A (en) * | 2008-12-02 | 2009-05-06 | 黄德欢 | Preparing method of highly conductive lithium iron anode material of lithium ionic cell |
| CN101447566A (en) * | 2008-12-29 | 2009-06-03 | 清华大学深圳研究生院 | Li-ion battery positive electrode material with layered-spinel symbiotic structure and preparation method |
| CN102324514A (en) * | 2011-09-21 | 2012-01-18 | 江西博能新材料有限公司 | A kind of lithium ion battery tertiary cathode material is with the preparation method of presoma |
| CN109052491A (en) * | 2018-07-23 | 2018-12-21 | 安徽工业大学 | A kind of preparation method of the porous high entropy oxide material of lithium ion battery negative material spinel-type |
| CN110190259A (en) * | 2019-06-12 | 2019-08-30 | 四川大学 | A kind of preparation method and lithium ion battery negative material of the high entropy oxide of nanometer |
| CN111082026A (en) * | 2019-12-31 | 2020-04-28 | 中南大学 | Ternary cathode material coated with lithium tungstate and preparation method thereof |
| CN112331840A (en) * | 2020-11-02 | 2021-02-05 | 中钢集团南京新材料研究院有限公司 | Nickel-cobalt-rich high-entropy ceramic cathode material for lithium ion battery and preparation method thereof |
| CN112467119A (en) * | 2020-12-02 | 2021-03-09 | 东北大学秦皇岛分校 | Preparation method and application of layered high-entropy oxide sodium-ion battery positive electrode material |
| CN112928252A (en) * | 2021-01-22 | 2021-06-08 | 中国科学院过程工程研究所 | Sodium-ion battery positive electrode material and preparation method and application thereof |
| CN113003615A (en) * | 2021-02-10 | 2021-06-22 | 中国科学院宁波材料技术与工程研究所 | High-entropy cathode material and preparation method and application thereof |
-
2021
- 2021-08-23 CN CN202110965375.1A patent/CN113871611B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101425576A (en) * | 2008-12-02 | 2009-05-06 | 黄德欢 | Preparing method of highly conductive lithium iron anode material of lithium ionic cell |
| CN101447566A (en) * | 2008-12-29 | 2009-06-03 | 清华大学深圳研究生院 | Li-ion battery positive electrode material with layered-spinel symbiotic structure and preparation method |
| CN102324514A (en) * | 2011-09-21 | 2012-01-18 | 江西博能新材料有限公司 | A kind of lithium ion battery tertiary cathode material is with the preparation method of presoma |
| CN109052491A (en) * | 2018-07-23 | 2018-12-21 | 安徽工业大学 | A kind of preparation method of the porous high entropy oxide material of lithium ion battery negative material spinel-type |
| CN110190259A (en) * | 2019-06-12 | 2019-08-30 | 四川大学 | A kind of preparation method and lithium ion battery negative material of the high entropy oxide of nanometer |
| CN111082026A (en) * | 2019-12-31 | 2020-04-28 | 中南大学 | Ternary cathode material coated with lithium tungstate and preparation method thereof |
| CN112331840A (en) * | 2020-11-02 | 2021-02-05 | 中钢集团南京新材料研究院有限公司 | Nickel-cobalt-rich high-entropy ceramic cathode material for lithium ion battery and preparation method thereof |
| CN112467119A (en) * | 2020-12-02 | 2021-03-09 | 东北大学秦皇岛分校 | Preparation method and application of layered high-entropy oxide sodium-ion battery positive electrode material |
| CN112928252A (en) * | 2021-01-22 | 2021-06-08 | 中国科学院过程工程研究所 | Sodium-ion battery positive electrode material and preparation method and application thereof |
| CN113003615A (en) * | 2021-02-10 | 2021-06-22 | 中国科学院宁波材料技术与工程研究所 | High-entropy cathode material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈克丕;李泽民;马金旭;刘腾飞;张建军;李翠伟;张孝文;: "高熵陶瓷材料研究进展与展望", 陶瓷学报, vol. 41, no. 02 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114883522A (en) * | 2022-04-20 | 2022-08-09 | 南京邮电大学 | High-entropy-like multi-element layered transition metal oxide cathode material and preparation method and application thereof |
| CN115050940A (en) * | 2022-06-21 | 2022-09-13 | 北京理工大学重庆创新中心 | High-entropy ceramic modified cathode material and preparation method and application thereof |
| CN115050940B (en) * | 2022-06-21 | 2023-08-11 | 北京理工大学重庆创新中心 | High-entropy ceramic modified cathode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113871611B (en) | 2023-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110459736B (en) | Positive electrode material, positive electrode plate containing positive electrode material and lithium ion battery | |
| CN110931797A (en) | High-nickel positive electrode material with composite coating layer and preparation method thereof | |
| CN102024947B (en) | LiFePO4/Li-Al-O composite positive electrode material and preparation method thereof | |
| CN110112388B (en) | Porous tungsten trioxide coated modified positive electrode material and preparation method thereof | |
| CN106410170B (en) | Anode material for compound lithium ion battery and preparation method thereof and lithium ion battery | |
| CN111092220A (en) | M-element bulk phase doped modified manganese-based positive electrode material of tunnel-type sodium-ion battery and preparation method thereof | |
| CN113937286B (en) | Coated modified sodium ion battery positive electrode material, preparation method thereof and battery | |
| CN113871611B (en) | Preparation method of high-entropy oxide material composite ternary material | |
| CN113540466B (en) | Metal boride and borate composite coated modified nickel-cobalt-manganese ternary material precursor and preparation method thereof | |
| CN108091854A (en) | A kind of high-voltage spinel type anode material for lithium-ion batteries of Anion-cation multiple dope and preparation method thereof | |
| CN112993229A (en) | Preparation method of multi-metal MOF gradient coated modified ternary precursor | |
| CN115172709A (en) | High-performance strontium-doped ternary sodium-ion battery positive electrode material and preparation method thereof | |
| WO2019080310A1 (en) | Molybdenum-doped lithium-rich manganese-based cathode material and preparation method therefor | |
| CN113488629B (en) | Spherical carbon-coated tungsten oxide/sulfur positive electrode material of core-shell structure loaded with multiple rare earth oxides and preparation method thereof | |
| CN116759583B (en) | Coating modified precursor, preparation method thereof, positive electrode material and lithium ion battery | |
| WO2019104948A1 (en) | Molybdenum doping-modified lithium manganese oxide composite material, preparation method therefor and lithium ion battery | |
| CN117219772A (en) | Sodium ion battery positive electrode material with low-nickel shell structure and preparation method thereof | |
| CN109659538B (en) | Preparation of rich lithium manganese-based oxide material based on coating of dopamine and lithium phosphate, product and application thereof | |
| CN115498158B (en) | Coated modified spinel lithium manganate material and preparation method and application thereof | |
| CN107834054B (en) | Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery | |
| CN111613792A (en) | Nickel-containing oxide electrode material and preparation, application and storage methods thereof | |
| CN115312754A (en) | Lamellar cobalt-free lithium-rich manganese-based positive electrode material and preparation method and application thereof | |
| CN111313008B (en) | Magnesium-containing lithium-rich manganese-based positive electrode and preparation method thereof | |
| CN111883746B (en) | Modified lithium-rich manganese-based oxide positive electrode material and preparation method and application thereof | |
| CN114864916A (en) | Niobium pentoxide coated graphite composite negative electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |