CN117954595A - High-voltage monocrystal ternary positive electrode material and preparation method thereof - Google Patents
High-voltage monocrystal ternary positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN117954595A CN117954595A CN202311873846.1A CN202311873846A CN117954595A CN 117954595 A CN117954595 A CN 117954595A CN 202311873846 A CN202311873846 A CN 202311873846A CN 117954595 A CN117954595 A CN 117954595A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- metal organic
- electrode material
- organic framework
- glassy metal
- 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.)
- Pending
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000005300 metallic glass Substances 0.000 claims abstract description 80
- 239000013384 organic framework Substances 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000010405 anode material Substances 0.000 claims abstract description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 239000011159 matrix material Substances 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 238000005253 cladding Methods 0.000 claims abstract description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 68
- 238000010438 heat treatment Methods 0.000 claims description 65
- 239000002243 precursor Substances 0.000 claims description 41
- 239000012621 metal-organic framework Substances 0.000 claims description 32
- 239000010406 cathode material Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 28
- 239000013078 crystal Substances 0.000 claims description 25
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 11
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 11
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims description 3
- 229910013716 LiNi Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims 1
- 229910052734 helium Inorganic materials 0.000 claims 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 1
- 229910052754 neon Inorganic materials 0.000 claims 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 21
- 230000002427 irreversible effect Effects 0.000 abstract description 9
- 230000001351 cycling effect Effects 0.000 abstract description 6
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 40
- 238000003756 stirring Methods 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- -1 polypropylene Polymers 0.000 description 11
- 229910013870 LiPF 6 Inorganic materials 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 10
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 10
- 239000012982 microporous membrane Substances 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 238000011056 performance test Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 8
- 239000005373 porous glass Substances 0.000 description 6
- 229910012888 LiNi0.6Co0.1Mn0.3O2 Inorganic materials 0.000 description 5
- 229910011624 LiNi0.7Co0.1Mn0.2O2 Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 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
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion secondary battery materials, and discloses a high-voltage monocrystal ternary positive electrode material and a preparation method thereof. The positive electrode material comprises a matrix material and a coating material coated on the surface of the matrix material; the matrix material is a monocrystal ternary anode material; the cladding material comprises a porous glassy metal organic framework; oxygen vacancies exist on the surface of the positive electrode material; wherein, the mass ratio of the porous glassy metal organic framework to the monocrystal ternary positive electrode material is 1:200-5000. The coating material in the positive electrode material of the invention forms oxygen vacancies on the surface of the matrix material, and the unique topological structure of the coating material effectively inhibits irreversible oxygen loss; the porous glassy metal organic frame coating material provides rich lithium ion transmission channels, improves the diffusion of lithium ions, enhances the conductivity of ions, and improves the cycling stability and the multiplying power performance of the anode material under high pressure.
Description
Technical Field
The invention relates to the technical field of lithium ion secondary battery materials, in particular to a high-voltage monocrystal ternary positive electrode material and a preparation method thereof.
Background
The lithium ion battery as a novel energy storage device has the advantages of high working voltage, long cycle life, no memory effect, small environmental pollution and the like, and is widely applied to the fields of various electronic consumer products and power automobiles. The battery of the high-end electronic product in the market is updated into a high-voltage battery core, and the energy density of the battery is obviously improved along with the improvement of charging voltage, so that the battery has great significance in meeting the higher volumetric specific energy and the endurance requirement of the high-end portable equipment. The performance of a lithium ion battery is closely related to the performance of the positive electrode material.
With the increasing requirements of the market on energy density, ternary materials become one of hot spots for research of positive electrode materials, and single crystal ternary positive electrode materials are paid attention to in the field of high-voltage application in recent years due to high thermal stability and phase stability. However, when the monocrystal ternary positive electrode material works under higher voltage, irreversible oxygen loss exists, and meanwhile, side reactions of the positive electrode material and electrolyte are aggravated, so that the problems of continuous decomposition of the electrolyte, corrosion of the electrode material and the like are caused, the rate performance and the cycle life are further reduced, and the large-scale application of the monocrystal ternary positive electrode material is seriously hindered.
Since the surface of the positive electrode material has irreversible oxygen loss and side reaction between the positive electrode material and the electrolyte, surface modification is an effective method for solving the problems, and many reported surface modification means aim to improve the cycle performance, and the surface modification method has little effect on improving the irreversible oxygen loss and side reaction problems of the single crystal ternary positive electrode material under high pressure.
Therefore, it is desirable to provide a method for preparing a surface modified single crystal ternary positive electrode material that improves material cycle performance and oxygen loss performance at high voltages.
Disclosure of Invention
The invention aims to solve the problem of oxygen loss of a monocrystal ternary anode material under high voltage in the prior art, and provides an anode material and a preparation method thereof. According to the invention, the porous glass metal organic frame is coated on the surface of the monocrystal ternary cathode material, and oxygen vacancies are formed on the surface of the monocrystal ternary cathode material by the coated porous glass metal organic frame, so that the unique topological structure of the porous glass metal organic frame can effectively inhibit irreversible oxygen loss, improve the diffusion of lithium ions, enhance the ion conductivity and improve the stability of the cathode material under high pressure.
In order to achieve the above object, a first aspect of the present invention provides a positive electrode material, which includes a base material and a coating material coated on a surface of the base material; the matrix material is a monocrystal ternary anode material; the cladding material comprises a porous glassy metal organic framework; oxygen vacancies exist on the surface of the positive electrode material;
Wherein, the mass ratio of the porous glassy metal organic framework to the monocrystal ternary positive electrode material is 1:200-5000.
The second aspect of the present invention provides a method for preparing a positive electrode material, wherein the method comprises the steps of:
(1) Mixing imidazole, MOF metal organic framework material and solvent, and then filtering and drying to obtain porous glassy metal organic framework precursor;
(2) Mixing the porous glassy metal organic frame precursor with a monocrystal ternary anode material, and then performing heat treatment to obtain the anode material;
wherein, the mass ratio of the porous glassy metal organic framework to the monocrystal ternary anode material is 1:200-5000.
In a third aspect, the present invention provides a positive electrode material prepared by the method according to the second aspect.
A fourth aspect of the present invention provides a use of the positive electrode material of the first and third aspects in a lithium ion battery.
Through the technical scheme, the invention has the following beneficial effects:
(1) According to the positive electrode material provided by the invention, the porous glass state metal organic framework is coated on the surface of the monocrystal ternary positive electrode material, and oxygen vacancies are formed on the surface of the monocrystal ternary positive electrode material by the coated porous glass state metal organic framework, so that irreversible oxygen loss is effectively inhibited by the unique topological structure; the porous glassy metal organic framework provides rich lithium ion transmission channels, improves the diffusion of lithium ions and enhances the conductivity of ions, so that the cycling stability and the multiplying power performance of the positive electrode material under high pressure are improved;
(2) According to the positive electrode material, the porous glassy metal organic frame with the surface coated effectively isolates the direct contact between the monocrystal ternary positive electrode material and the electrolyte, so that the occurrence of interface side reaction of the monocrystal ternary positive electrode material in a battery system is avoided, and the corrosion of the electrolyte to the monocrystal ternary positive electrode material is reduced;
(3) The cathode material provided by the invention has the gram capacity of 195-203mAh/g at 0.5C, the first charge-discharge efficiency of 89-90.5%, the cycle capacity retention rate of 1C cycle of 50 circles of 93-95.5%, excellent cycle performance under high voltage, simple and easy preparation method, low production cost and wide industrial application value.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention.
FIG. 1 is a schematic view of a positive electrode material provided by the present invention;
FIG. 2 is an SEM image of the positive electrode material prepared in example 1 of the present invention;
Fig. 3 is a graph showing comparison of cycle performance curves of lithium ion batteries prepared from the positive electrode materials prepared in example 1, example 5, comparative example 1 and comparative example 2 according to the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a positive electrode material, which comprises a matrix material and a coating material coated on the surface of the matrix material; the matrix material is a monocrystal ternary anode material; the cladding material comprises a porous glassy metal organic framework; oxygen vacancies exist on the surface of the positive electrode material;
Wherein, the mass ratio of the porous glassy metal organic framework to the monocrystal ternary positive electrode material is 1:200-5000.
The structure diagram of the positive electrode material provided by the invention is shown in figure 1, the positive electrode material comprises a matrix material and a coating material coated on the surface of the matrix material, wherein the coating material forms oxygen vacancies on the surface of the matrix material, and the unique topological structure of the coating material is beneficial to inhibiting irreversible oxygen loss, improving the diffusion of lithium ions and enhancing the conductivity, so that the cycling stability of the positive electrode material under high voltage is improved. In the invention, in the porous glassy metal organic framework coated by the positive electrode material, O 2- in the material is oxidized to form O 2 in the charge and discharge process, and the O 2 leaves the system to form oxygen vacancies. In the present invention, oxygen vacancies existing at the surface of the positive electrode material are characterized by X-ray photoelectron spectroscopy (XPS).
In some embodiments of the present invention, preferably, the mass ratio of the porous glassy metal organic framework precursor to the single crystal ternary cathode material is 1:200-5000, for example, may be 1: 200. 1: 500. 1: 1000. 1: 1500. 1: 2000. 1: 2500. 1: 3000. 1: 3500. 1: 4000. 1: 4500. 1:5000, and any value in the range of any two values, preferably 1:500-3000, more preferably 1:1000-2000. In the invention, the mass ratio of the porous glassy metal organic framework precursor to the monocrystal ternary cathode material is controlled within the range, so that the obtained porous glassy metal organic framework coated cathode material has excellent cycle stability and rate capability under high pressure. The mass ratio of the porous glassy metal organic framework precursor to the monocrystal ternary positive electrode material is greater than 1:200, excessive porous glassy metal organic framework precursor, too thick coating layer on the surface of the monocrystal ternary positive electrode material, and reduced performance of the positive electrode material under high voltage, resulting in capacity loss; the mass ratio of the porous glassy metal organic framework precursor to the monocrystal ternary positive electrode material is less than 1:5000, too few porous glassy metal organic framework precursors can not completely coat the monocrystal ternary cathode material, so that the performance of the cathode material is reduced under high voltage, and the cycle performance under high voltage can not be improved.
In the present invention, the single crystal ternary cathode material may be any single crystal ternary cathode material known to those skilled in the art, preferably, the single crystal ternary cathode material has a chemical formula of LiNi xCoyMn1-x-yO2, wherein 0 < x < 1,0 < y < 1, and x+y < 1, more preferably, 0.6. Ltoreq.x < 1, and 0 < y < 0.2.
In the invention, the higher the nickel content in the monocrystal ternary anode material is, the cycle performance of the battery is relatively reduced; the lower the nickel content in the single crystal ternary cathode material is, the relatively reduced the capacity of the battery. According to the invention, the porous glassy metal organic frame is coated on the surface of the monocrystal ternary positive electrode material, so that the direct contact between the monocrystal ternary positive electrode material and electrolyte is effectively isolated, and the occurrence of interface side reaction of the monocrystal ternary positive electrode material in a battery system is avoided; the coated porous glassy metal organic framework forms oxygen vacancies on the surface of the monocrystal ternary cathode material, and the unique topological structure of the porous glassy metal organic framework effectively inhibits irreversible oxygen loss; the coated porous glassy metal organic framework provides rich lithium ion transmission channels, improves the diffusion of lithium ions, and improves the cycling stability and the rate capability of the anode material under high pressure.
The second aspect of the present invention provides a method for preparing a positive electrode material, wherein the method comprises the steps of:
(1) Mixing imidazole, MOF metal organic framework material and solvent, and then filtering and drying to obtain porous glassy metal organic framework precursor;
(2) Mixing the porous glassy metal organic frame precursor with a monocrystal ternary anode material, and then performing heat treatment to obtain the anode material;
wherein, the mass ratio of the porous glassy metal organic framework to the monocrystal ternary anode material is 1:200-5000.
In some embodiments of the invention, preferably, the mass ratio of imidazole to MOF metal organic framework material is from 2 to 10:0.05-0.2, preferably 3-5:0.1-0.15. In the invention, the mass ratio of the imidazole to the MOF metal organic framework material is controlled in the range, which is favorable for obtaining the porous glassy metal organic framework precursor, thereby being favorable for obtaining the porous glassy metal organic framework coated anode material and improving the cycle stability and the multiplying power performance of the anode material under high pressure. Excessive MOF metal organic framework material can reduce gram capacity of the positive electrode material, and cause poor cycle performance and increased DCR; too little MOF metal organic framework material can result in poor cycling performance of the positive electrode material at high voltages. The metal organic frame material is too much or too little, the porous glassy metal organic frame coating layer cannot be obtained, and the obtained positive electrode material cannot achieve the above technical effects.
In some embodiments of the invention, preferably, the imidazole has a mass to solvent volume ratio of 2 to 10g:8-45mL, preferably 3-5g:16-25mL.
In some embodiments of the present invention, preferably, the mass ratio of the porous glassy metal organic framework precursor to the single crystal ternary cathode material is 1:200-5000, preferably 1:5000-3000, more preferably 1:1000-2000. In the invention, the mass ratio of the porous glassy metal organic framework precursor to the monocrystal ternary positive electrode material is controlled within the range, so that the cycling stability and the multiplying power performance of the positive electrode material under high pressure are improved.
In the present invention, the MOF metal-organic framework material has the conventional definition in the art, and various MOF metal-organic framework materials conventionally used in the art CAN be used in the present invention, and in some embodiments of the present invention, it is preferable that the MOF metal-organic framework material is a zeolitic imidazolate framework material, preferably at least one selected from the group consisting of ZIF-8, GIS, AFI and CAN.
In some embodiments of the present invention, preferably, the solvent is a polar organic solvent, preferably at least one selected from n-butanol, iso-butanol and sec-butanol, more preferably n-butanol.
In the present invention, in the step (1), the imidazole, the metal organic framework material and the solvent are mixed, wherein the mixing process includes, but is not limited to, at least one of a mixing manner such as stirring mixing, ultrasonic dispersion mixing, and the like, preferably, the mixing manner is ultrasonic dispersion, wherein the condition of ultrasonic dispersion is not particularly limited as long as the imidazole and the metal organic framework material can be completely dissolved in the solvent, preferably, the condition of ultrasonic dispersion includes: the frequency of ultrasonic dispersion is 18-30kHz, preferably 20-25kHz; the time of ultrasonic dispersion is 1-10 hours, preferably 5-8 hours.
In the present invention, the imidazole, the metal organic framework material and the solvent are mixed and then subjected to filtration and drying treatment, wherein the drying condition is not particularly limited as long as the drying can be ensured to obtain the porous glassy metal organic framework precursor, preferably, the drying can be performed in a vacuum drying oven, the drying temperature can be 50-200 ℃ for 5-50 hours, more preferably, the drying can be performed at 100-150 ℃ for 10-12 hours.
In the present invention, in the step (2), the porous glassy metal organic frame material is mixed with the single-crystal ternary cathode material, wherein the mixing process includes, but is not limited to, at least one of a mixing manner such as sieving mixing, stirring mixing, ultrasonic dispersion mixing, etc., and preferably the mixing is performed under stirring conditions, wherein the stirring conditions are not particularly limited as long as the porous glassy metal organic frame material and the single-crystal ternary cathode material can be uniformly mixed, and for example, can be performed under stirring conditions of 200 to 1000 r/min.
In the present invention, in step (2), after the porous glassy metal organic frame precursor and the single crystal ternary cathode material are mixed, heat treatment is performed, where the heat treatment is favorable for obtaining a cathode material coated by the porous glassy metal organic frame, and preferably, the heat treatment conditions include: under inert gas, the heat treatment temperature is 200-800 ℃, preferably 300-500 ℃; the heating rate is 1-20 ℃/min, preferably 2-10 ℃/min; the heat treatment time is 4.5-15 hours, preferably 5-12 hours.
In the present invention, the temperature of the heat treatment and the time of the heat treatment are controlled within the above ranges, which is advantageous for obtaining the porous glassy metal organic frame-coated positive electrode material. The heat treatment temperature is too low to achieve the desired treatment effect; the heat treatment temperature is too high, and the porous glassy metal organic framework precursor coating agent can be fused into the monocrystal ternary anode material to destroy the structure; the heat treatment time is too short to achieve the effect of expected structural optimization; too long a heat treatment time can cause the collapse of the framework and cannot well maintain the morphology of the porous glassy metal organic framework layer.
In the present invention, the heat treatment is performed under an inert gas, preferably selected from argon and/or nitrogen, preferably argon. The flow rate of the inert gas is 10-50mL/min, and the flow rate is controlled in the range, so that the inert gas can effectively cover the surface of the material, and a stable atmosphere environment is maintained; too low a flow rate may lead to uneven atmosphere and failure to effectively protect the material; too high a flow rate may cause disturbance of the atmosphere, affecting the coating effect.
According to a preferred embodiment of the present invention, the method for preparing the positive electrode material comprises the steps of:
(1) The mass ratio is 2-10:0.05-0.2 of imidazole and metal organic frame materials are weighed, mixed with solvent by ultrasonic stirring, and then filtered and dried to obtain porous glassy metal organic frame precursor;
(2) And mixing the porous glassy metal organic framework precursor with a monocrystal ternary positive electrode material according to the mass ratio of 1: mixing 200-5000, and performing heat treatment at 200-800 ℃ for 4.5-15h under inert gas to obtain the positive electrode material.
In a third aspect, the present invention provides a positive electrode material prepared by the method according to the second aspect.
In the invention, the gram capacity of the ternary positive electrode material at 0.5C is 195-203mAh/g, preferably 195.8-202.1mAh/g; the first charge-discharge efficiency is 89-90.5%, preferably 89.7-90.1%; the retention rate of the circulation capacity of 50 circles of the 1C circulation reaches 93 to 95.5 percent, preferably 93.9 to 95 percent. The gram capacity of 0.5C is tested by adopting a blue electric test cabinet; the first charge and discharge efficiency is tested by adopting a blue electricity test cabinet; the cycle capacity retention rate at 50 cycles of 1C was the ratio of the discharge capacity at 50 th cycle to the discharge capacity at 1 st cycle.
In the invention, oxygen vacancies exist on the surface of the positive electrode material, the unique topological structure of the positive electrode material effectively inhibits irreversible oxygen loss, a rich lithium ion transmission channel is provided, the diffusion of lithium ions is improved, the conductivity of ions is enhanced, and the cycle stability and the multiplying power performance of the positive electrode material under high pressure are improved.
A fourth aspect of the present invention provides a use of the positive electrode material of the first and third aspects in a lithium ion battery.
The present invention will be described in detail by examples.
Example 1
(1) Weighing 3g of imidazole, 100mg of ZIF-8 and 20mL of n-butanol, placing in a beaker, carrying out ultrasonic stirring at 25kHz for 5h, filtering, placing in an oven, heating to 150 ℃ at a heating rate of 2 ℃/min, and drying for 12h to obtain a porous glassy metal organic framework precursor;
(2) And (3) stirring and mixing 1g of the porous glassy metal organic frame precursor and 1000g of the anode material LiNi 0.6Co0.1Mn0.3O2, placing the mixture in an atmosphere furnace for heat treatment after the mixture is completed, introducing argon, heating to 500 ℃ at a heating rate of 2 ℃/min, preserving heat for 10 hours, cooling to room temperature after the heat treatment is completed, and obtaining the anode material coated by the porous glassy metal organic frame, wherein oxygen vacancies exist on the surface of the anode material through XPS test.
(3) The positive electrode material is taken as a positive electrode, a metal lithium sheet is taken as a negative electrode, a 1mol/L LiPF 6 solution is taken as an electrolyte, a Celgard 2325 polypropylene microporous membrane is taken as a diaphragm, the battery is assembled into a 2032 button battery, the electrochemical performance of the battery is tested, the test voltage is 3-4.5V, the test temperature is 25 ℃, and the test results are shown in Table 1.
Fig. 2 is an SEM image of the positive electrode material prepared in this example, from which it can be seen that the porous glassy metal-organic framework coats the single-crystal ternary positive electrode material, and the ternary positive electrode material has a single-crystal morphology, and the porous glassy metal-organic framework is observed to be uniformly coated by TEM.
Fig. 3 is a graph showing comparison of cycle performance curves of lithium ion batteries prepared from the prepared cathode materials, and it can be seen from the graph that the cathode materials prepared in this example have excellent cycle stability.
Example 2
(1) Weighing 5g of imidazole, 150mg of ZIF-8 and 30mL of n-butanol, placing in a beaker, performing ultrasonic stirring at 22kHz for 7h, filtering, placing in an oven, heating to 150 ℃ at a heating rate of 2 ℃/min, and drying for 12h to obtain a porous glassy metal organic framework precursor;
(2) And stirring and mixing 1g of the porous glassy metal organic frame precursor and 2000g of the anode material LiNi 0.6Co0.1Mn0.3O2, placing the mixture in an atmosphere furnace for heat treatment, introducing argon, heating to 300 ℃ at a heating rate of 2 ℃/min, preserving heat for 12 hours, cooling to room temperature after the heat treatment is finished, and obtaining the anode material coated by the porous glassy metal organic frame, wherein oxygen vacancies exist on the surface of the anode material through XPS test.
(3) The positive electrode material is taken as a positive electrode, a metal lithium sheet is taken as a negative electrode, a 1mol/L LiPF 6 solution is taken as an electrolyte, a Celgard 2325 polypropylene microporous membrane is taken as a diaphragm, a 2032 button cell is assembled, the cell is subjected to electrochemical performance test, the test voltage is 3-4.5V, the test temperature is 25 ℃, and the test results are shown in Table 1.
Example 3
(1) Weighing 3g of imidazole, 80mg of ZIF-8 and 40mL of n-butanol, placing in a beaker, carrying out ultrasonic stirring at 20kHz for 8 hours, filtering, placing in a baking oven, heating to 100 ℃ at a heating rate of 2 ℃/min, and drying for 15 hours to obtain a porous glassy metal organic framework precursor;
(2) And 3g of the porous glassy metal organic frame precursor and 1000g of the positive electrode material LiNi 0.6Co0.1Mn0.3O2 are stirred and mixed, after the mixing is completed, the mixture is placed in an atmosphere furnace for heat treatment, argon is introduced, the temperature is raised to 550 ℃ at a heating rate of 2 ℃/min, the heat is preserved for 8 hours, after the heat treatment is completed, the mixture is cooled to room temperature, and the porous glassy metal organic frame-coated positive electrode material is obtained, and through XPS test, oxygen vacancies exist on the surface of the positive electrode material.
(3) The positive electrode material is taken as a positive electrode, a metal lithium sheet is taken as a negative electrode, a 1mol/L LiPF 6 solution is taken as an electrolyte, a Celgard 2325 polypropylene microporous membrane is taken as a diaphragm, a 2032 button cell is assembled, the cell is subjected to electrochemical performance test, the test voltage is 3-4.5V, the test temperature is 25 ℃, and the test results are shown in Table 1.
Example 4
(1) Weighing 5g of imidazole, 60mg of ZIF-8 and 35mL of n-butanol, placing in a beaker, carrying out ultrasonic stirring at 25kHz for 6h, filtering, placing in a baking oven, heating to 180 ℃ at a heating rate of 2 ℃/min, and drying for 15h to obtain a porous glassy metal organic framework precursor;
(2) And 5g of the porous glassy metal organic frame precursor and 1000g of the positive electrode material LiNi 0.6Co0.1Mn0.3O2 are stirred and mixed, after the mixing is completed, the mixture is placed in an atmosphere furnace for heat treatment, argon is introduced, the temperature is raised to 600 ℃ at the heating rate of 2 ℃/min, the heat is preserved for 10 hours, after the heat treatment is completed, the mixture is cooled to room temperature, and the porous glassy metal organic frame-coated positive electrode material is obtained, and through XPS test, oxygen vacancies exist on the surface of the positive electrode material.
(3) The positive electrode material is taken as a positive electrode, a metal lithium sheet is taken as a negative electrode, a 1mol/L LiPF 6 solution is taken as an electrolyte, a Celgard 2325 polypropylene microporous membrane is taken as a diaphragm, a 2032 button cell is assembled, the cell is subjected to electrochemical performance test, the test voltage is 3-4.5V, the test temperature is 25 ℃, and the test results are shown in Table 1.
Example 5
(1) Weighing 3g of imidazole, 100mg of ZIF-8 and 20mL of n-butanol, placing in a beaker, performing ultrasonic stirring at 22kHz for 5 hours, filtering, placing in an oven, heating to 150 ℃ at a heating rate of 2 ℃/min, and drying for 12 hours to obtain a porous glassy metal organic framework precursor;
(2) And (3) stirring and mixing 1g of the porous glassy metal organic frame precursor and 1000g of the anode material LiNi 0.7Co0.1Mn0.2O2, placing the mixture in an atmosphere furnace for heat treatment after the mixture is completed, introducing argon, heating to 500 ℃ at a heating rate of 2 ℃/min, preserving heat for 10 hours, cooling to room temperature after the heat treatment is completed, and obtaining the anode material coated by the porous glassy metal organic frame, wherein oxygen vacancies exist on the surface of the anode material through XPS test.
(3) The positive electrode material is taken as a positive electrode, a metal lithium sheet is taken as a negative electrode, a 1mol/L LiPF 6 solution is taken as an electrolyte, a Celgard 2325 polypropylene microporous membrane is taken as a diaphragm, a 2032 button cell is assembled, the cell is subjected to electrochemical performance test, the test voltage is 3-4.5V, the test temperature is 25 ℃, and the test results are shown in Table 1.
Fig. 3 is a graph showing comparison of cycle performance curves of lithium ion batteries prepared from the prepared cathode materials, and it can be seen from the graph that the cathode materials prepared in this example have excellent cycle stability.
Example 6
(1) Weighing 4g of imidazole, 120mg of ZIF-8 and 25mL of n-butanol, placing in a beaker, performing ultrasonic stirring at 22kHz for 8 hours, filtering, placing in a baking oven, heating to 100 ℃ at a heating rate of 2 ℃/min, and drying for 12 hours to obtain a porous glassy metal organic framework precursor;
(2) And stirring and mixing 1g of the porous glassy metal organic frame precursor and 1500g of the anode material LiNi 0.7Co0.1Mn0.2O2, placing the mixture in an atmosphere furnace for heat treatment, introducing argon, heating to 400 ℃ at a heating rate of 2 ℃/min, preserving heat for 10 hours, cooling to room temperature after the heat treatment is finished, and obtaining the anode material coated by the porous glassy metal organic frame, wherein oxygen vacancies exist on the surface of the anode material through XPS test.
(3) The positive electrode material is taken as a positive electrode, a metal lithium sheet is taken as a negative electrode, a 1mol/L LiPF 6 solution is taken as an electrolyte, a Celgard 2325 polypropylene microporous membrane is taken as a diaphragm, a 2032 button cell is assembled, the cell is subjected to electrochemical performance test, the test voltage is 3-4.5V, the test temperature is 25 ℃, and the test results are shown in Table 1.
Example 7
(1) Weighing 6g of imidazole, 80mg of ZIF-8 and 20mL of n-butanol, placing in a beaker, carrying out ultrasonic stirring at 30kHz for 4 hours, filtering, placing in a baking oven, heating to 120 ℃ at a heating rate of 2 ℃/min, and drying for 10 hours to obtain a porous glassy metal organic framework precursor;
(2) And 3g of the porous glassy metal organic frame precursor and 700g of the anode material LiNi 0.7Co0.1Mn0.2O2 are stirred and mixed, after the mixing is completed, the mixture is placed in an atmosphere furnace for heat treatment, argon is introduced, the temperature is raised to 450 ℃ at the heating rate of 2 ℃/min, the heat is preserved for 8 hours, after the heat treatment is completed, the mixture is cooled to room temperature, and the anode material coated by the porous glassy metal organic frame is obtained, and through XPS test, oxygen vacancies exist on the surface of the anode material.
(3) The positive electrode material is taken as a positive electrode, a metal lithium sheet is taken as a negative electrode, a 1mol/L LiPF 6 solution is taken as an electrolyte, a Celgard 2325 polypropylene microporous membrane is taken as a diaphragm, a 2032 button cell is assembled, the cell is subjected to electrochemical performance test, the test voltage is 3-4.5V, the test temperature is 25 ℃, and the test results are shown in Table 1.
Example 8
(1) Weighing 4g of imidazole, 60mg of ZIF-8 and 40mL of n-butanol, placing in a beaker, carrying out ultrasonic stirring at 28kHz for 7h, filtering, placing in a baking oven, heating to 150 ℃ at a heating rate of 2 ℃/min, and drying for 15h to obtain a porous glassy metal organic framework precursor;
(2) And 5g of the porous glassy metal organic frame precursor and 1000g of the positive electrode material LiNi 0.7Co0.1Mn0.2O2 are stirred and mixed, after the mixing is completed, the mixture is placed in an atmosphere furnace for heat treatment, argon is introduced, the temperature is raised to 750 ℃ at a heating rate of 2 ℃/min, the heat is preserved for 6 hours, after the heat treatment is completed, the mixture is cooled to room temperature, and the porous glassy metal organic frame-coated positive electrode material is obtained, and through XPS test, oxygen vacancies exist on the surface of the positive electrode material.
(3) The positive electrode material is taken as a positive electrode, a metal lithium sheet is taken as a negative electrode, a 1mol/L LiPF 6 solution is taken as an electrolyte, a Celgard 2325 polypropylene microporous membrane is taken as a diaphragm, a 2032 button cell is assembled, the cell is subjected to electrochemical performance test, the test voltage is 3-4.5V, the test temperature is 25 ℃, and the test results are shown in Table 1.
Example 9
The procedure described in example 1 was followed, except,
In the step (1), the use amount of ZIF-8 of 100mg was changed to 180mg.
Example 10
The procedure described in example 1 was followed, except,
In the step (3), the dosage of 1g of the porous glass state metal organic framework precursor is changed to 3g.
Comparative example 1
The monocrystal ternary anode material LiNi 0.6Co0.1Mn0.3O2 is used as an anode, a metal lithium sheet is used as a cathode, a 1mol/L LiPF 6 solution is used as an electrolyte, a Celgard 2325 polypropylene microporous membrane is used as a diaphragm, a 2032 button cell is assembled, the cell is subjected to electrochemical performance test, the test voltage is 3-4.5V, the test temperature is 25 ℃, and the test result is shown in Table 1.
Fig. 3 is a graph showing the cycle performance curve of a lithium ion battery made of the prepared positive electrode material, and it can be seen from the graph that the positive electrode material prepared in this comparative example has poor cycle stability.
Comparative example 2
The monocrystal ternary anode material LiNi 0.7Co0.1Mn0.2O2 is used as an anode, a metal lithium sheet is used as a cathode, a 1mol/L LiPF 6 solution is used as an electrolyte, a Celgard 2325 polypropylene microporous membrane is used as a diaphragm, a 2032 button cell is assembled, the cell is subjected to electrochemical performance test, the test voltage is 3-4.5V, the test temperature is 25 ℃, and the test result is shown in Table 1.
Fig. 3 is a graph showing the cycle performance curve of a lithium ion battery made of the prepared positive electrode material, and it can be seen from the graph that the positive electrode material prepared in this comparative example has poor cycle stability.
TABLE 1
As can be seen from the results in Table 1, the porous glassy metal organic framework coated positive electrode material prepared by the method provided by the invention has the gram capacity of 195-203mAh/g at 0.5C, the first charge and discharge efficiency of 89-90.5%, the cycle capacity retention rate of 50 cycles of 1C of 93-95.5%, and excellent cycle performance under high voltage.
As can be seen from the combination of examples 1, 3, 4, 9, 10 and 1, the mass ratio of the porous glassy metal organic framework precursor to the single-crystal ternary cathode material in examples 3 and 4 is not within the preferred range, the mass ratio of imidazole to zeolite imidazole ester framework in example 9 is not within the preferred range, and the mass ratio of the porous glassy metal organic framework precursor to the single-crystal ternary cathode material in example 10 is not within the preferred range, so that gram capacity, first charge-discharge efficiency and cycle performance of the prepared cathode material at high voltage are slightly reduced;
As is clear from the combination of examples 5, 7, 8 and 1, the mass ratio of the porous glassy metal organic framework precursor to the single-crystal ternary cathode material in examples 7 and 8 is not within the preferred range, and the mass ratio of imidazole to the zeolitic imidazolate framework is not within the preferred range, so that the gram capacity, the first charge-discharge efficiency and the cycle performance of the prepared cathode material at high voltage are slightly reduced.
As can be seen from the combination of example 1, comparative example 1 and table 1, the conventional ternary single crystal positive electrode material adopted in comparative example 1 does not adopt the method provided by the invention to coat the porous glassy metal organic framework on the surface of the single crystal ternary positive electrode material; as can be seen from the combination of example 5, comparative example 2 and table 1, the conventional ternary single crystal positive electrode material adopted in comparative example 2 does not adopt the method provided by the invention to coat the porous glassy metal organic framework on the surface of the single crystal ternary positive electrode material, and the gram capacity of the single crystal ternary positive electrode materials in comparative example 1 and comparative example 2 under high voltage is lower, the initial charge and discharge efficiency is lower, the cycle capacity retention rate of 1C cycle for 50 cycles is lower, and the cycle performance under high voltage is poorer.
As can be seen from examples 1,2, 5,6 and table 1, the porous glassy metal organic framework coated positive electrode material prepared by the method provided by the invention has excellent cycle performance under high voltage.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The positive electrode material is characterized by comprising a matrix material and a coating material coated on the surface of the matrix material; the matrix material is a monocrystal ternary anode material; the cladding material comprises a porous glassy metal organic framework; oxygen vacancies exist on the surface of the positive electrode material;
Wherein, the mass ratio of the porous glassy metal organic framework to the monocrystal ternary positive electrode material is 1:200-5000.
2. The positive electrode material of claim 1, wherein the mass ratio of the porous glassy metal organic framework to the single crystal ternary positive electrode material is 1:500-3000, preferably 1:1000-2000.
3. The positive electrode material according to claim 1 or 2, wherein the single crystal ternary positive electrode material has a chemical formula of LiNi xCoyMn1-x-yO2, wherein 0 < x < 1,0 < y < 1, and x+y < 1.
4. The preparation method of the positive electrode material is characterized by comprising the following steps of:
(1) Mixing imidazole, MOF metal organic framework material and solvent, and then filtering and drying to obtain porous glassy metal organic framework precursor;
(2) Mixing the porous glassy metal organic frame precursor with a monocrystal ternary anode material, and then performing heat treatment to obtain the anode material;
wherein, the mass ratio of the porous glassy metal organic framework to the monocrystal ternary anode material is 1:200-5000.
5. The method of claim 4, wherein the mass ratio of imidazole to MOF metal organic framework material is 2-10:0.05-0.2, preferably 3-5:0.1-0.15;
Preferably, the mass to volume ratio of the imidazole to the solvent is 2-10g:8-45mL, preferably 3-5g:16-25mL;
preferably, the mass ratio of the porous glassy metal organic framework precursor to the single crystal ternary cathode material is 1:500-3000, preferably 1:1000-2000.
6. The method according to claim 4 or 5, wherein the MOF metal organic framework material is a zeolitic imidazolate framework material, preferably at least one selected from the group consisting of ZIF-8, GIS, AFI and CAN;
Preferably, the solvent is a polar organic solvent, preferably at least one selected from n-butanol, isobutanol and sec-butanol, more preferably n-butanol.
7. The method of any one of claims 4-6, wherein in step (1), the mixing is by ultrasonic dispersion;
Preferably, the conditions of ultrasonic dispersion include: the frequency of ultrasonic dispersion is 18-30kHz, preferably 20-25kHz; the ultrasonic dispersion time is 1-10h, preferably 5-8h;
Preferably, the drying temperature is 50-200 ℃ and the drying time is 5-50h.
8. The method of any of claims 4-7, wherein the heat treatment conditions comprise: under inert gas, the heat treatment temperature is 200-800 ℃, preferably 300-500 ℃; the heating rate is 1-20 ℃/min, preferably 2-10 ℃/min; the heat treatment time is 4.5-15h, preferably 5-12h;
Preferably, the inert gas is selected from at least one of argon, helium, neon and nitrogen.
9. A positive electrode material prepared by the method of any one of claims 4-8.
10. Use of the positive electrode material according to claims 1-3 and 9 in a lithium battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311873846.1A CN117954595A (en) | 2023-12-29 | 2023-12-29 | High-voltage monocrystal ternary positive electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311873846.1A CN117954595A (en) | 2023-12-29 | 2023-12-29 | High-voltage monocrystal ternary positive electrode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117954595A true CN117954595A (en) | 2024-04-30 |
Family
ID=90802969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311873846.1A Pending CN117954595A (en) | 2023-12-29 | 2023-12-29 | High-voltage monocrystal ternary positive electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117954595A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118352513A (en) * | 2024-06-17 | 2024-07-16 | 江苏蓝固新能源科技有限公司 | Glass-state MOFs coated positive electrode material, preparation method thereof and secondary battery |
-
2023
- 2023-12-29 CN CN202311873846.1A patent/CN117954595A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118352513A (en) * | 2024-06-17 | 2024-07-16 | 江苏蓝固新能源科技有限公司 | Glass-state MOFs coated positive electrode material, preparation method thereof and secondary battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20220052327A1 (en) | Anode material, electrochemical device and electronic device using the same | |
| KR100433822B1 (en) | Metal-coated carbon, preparation method thereof, and composite electrode and lithium secondary batteries comprising the same | |
| CN113054183A (en) | Preparation method of CoNi bimetal organic framework derived carbon-sulfur composite material | |
| CN110957477B (en) | Porous ceramic composite lithium metal cathode and preparation method thereof | |
| KR20160081692A (en) | Silicon-based anode active material, method of preparing the same, anode including the silicon-based anode active material, and lithium secondary battery including the anode | |
| CN110890530B (en) | Lithium metal secondary battery based on porous ceramic composite lithium metal cathode and preparation method thereof | |
| CN111646459A (en) | Preparation method and application of boron-doped graphene material | |
| CN117954595A (en) | High-voltage monocrystal ternary positive electrode material and preparation method thereof | |
| CN112670514A (en) | Double-coated lithium battery positive electrode material and preparation method thereof | |
| CN111916716A (en) | PVDF-TiO2Preparation method of composite membrane and application of composite membrane in inhibiting growth of lithium dendrite | |
| CN110592807B (en) | Thin film material for inhibiting growth of lithium dendrite and preparation method thereof | |
| CN110247041B (en) | ZnNiO/C composite nano material and preparation method thereof | |
| GB2621289A (en) | Method for preparing silicon-carbon composite negative electrode material and use thereof | |
| CN116504927A (en) | Lithium metal interface protection method and application thereof | |
| CN116014128A (en) | Lithium battery negative electrode material and preparation method thereof | |
| CN115642296A (en) | Inorganic-organic composite solid electrolyte lithium battery and preparation method thereof | |
| CN115360026A (en) | Preparation method of carbon-based composite high-entropy alloy CuAgCoCdZn lithium electrode material | |
| CN211017237U (en) | Porous ceramic composite lithium metal negative electrode and lithium metal secondary battery based on negative electrode | |
| CN114291802A (en) | Preparation and application of MOFs material modified lithium iron phosphate positive electrode material | |
| CN114023959A (en) | Preparation method of magnesium-containing novel graphene lithium ion battery cathode material | |
| CN111162259A (en) | Preparation method of copper-coated porous silicon composite material and composite electrode for lithium ion battery | |
| CN118367155B (en) | Foamed aluminum positive electrode current collector and preparation method and application thereof | |
| CN116462223B (en) | ZnS/MoO2Composite material and preparation method thereof, lithium-sulfur battery diaphragm and preparation method thereof, and lithium-sulfur battery | |
| CN117229525B (en) | Coating material of lithium ion battery anode material, and preparation method and application thereof | |
| CN114335476B (en) | Preparation method and application of anode material |
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 |