CN114649531A - Modified electrode and preparation method and application thereof - Google Patents
Modified electrode and preparation method and application thereof Download PDFInfo
- Publication number
- CN114649531A CN114649531A CN202011506787.0A CN202011506787A CN114649531A CN 114649531 A CN114649531 A CN 114649531A CN 202011506787 A CN202011506787 A CN 202011506787A CN 114649531 A CN114649531 A CN 114649531A
- Authority
- CN
- China
- Prior art keywords
- electrode
- modified
- gas
- metal
- thickness
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 66
- 238000012986 modification Methods 0.000 claims abstract description 52
- 230000004048 modification Effects 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 85
- 238000000151 deposition Methods 0.000 claims description 48
- 230000008021 deposition Effects 0.000 claims description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims description 36
- 239000011149 active material Substances 0.000 claims description 35
- 239000012159 carrier gas Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 239000011888 foil Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000000231 atomic layer deposition Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000011268 mixed slurry Substances 0.000 claims description 13
- 238000005096 rolling process Methods 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000004020 conductor Substances 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011164 primary particle Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000011163 secondary particle Substances 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims 1
- 239000011572 manganese Substances 0.000 description 44
- 238000012360 testing method Methods 0.000 description 43
- 238000010998 test method Methods 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 25
- 238000005520 cutting process Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229910013716 LiNi Inorganic materials 0.000 description 15
- 229910001873 dinitrogen Inorganic materials 0.000 description 13
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 238000002715 modification method Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 239000002000 Electrolyte additive Substances 0.000 description 3
- 229910010093 LiAlO Inorganic materials 0.000 description 3
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 3
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 3
- 229910006596 α−NaFeO2 Inorganic materials 0.000 description 3
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910010092 LiAlO2 Inorganic materials 0.000 description 2
- 229910015965 LiNi0.8Mn0.1Co0.1O2 Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910019573 CozO2 Inorganic materials 0.000 description 1
- 229910007848 Li2TiO3 Inorganic materials 0.000 description 1
- 229910007822 Li2ZrO3 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000009966 trimming 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the field of lithium batteries, and discloses a modified electrode and a preparation method and application thereof. The modified electrode comprises an electrode and a modification layer on the surface of the electrode, and the thickness of the electrode is not more than 150 micrometers; the modification layer contains a composite oxide of lithium and metal M, and the metal M is selected from at least one of Al, Ti, Zr, W, Ta and Hf; the thickness of the modification layer is 25-50 nm. The modified electrode is used in a lithium ion battery, and can reduce the internal resistance increasing rate and improve the cycle performance of the battery.
Description
Technical Field
The invention belongs to the field of lithium batteries, and particularly relates to a modified electrode, a preparation method thereof and application thereof in a lithium ion battery.
Background
As one of electrochemical energy storage devices with the most excellent performance at present, the lithium ion battery has the advantages of high energy density (200-300Wh/kg), long cycle life (more than or equal to 2000 times), low self-discharge, diversified flexibility and shape and the like, is widely applied to the fields of consumer electronics, intelligent robots, electric automobiles, large-scale energy storage and the like, and occupies an important position in national economy and human life.
At present, lithium cobaltate is the anode material mainly used by consumer electronic batteries, but cobalt is a metal which is relatively rare and expensive, and the mineral resources are extremely unevenly distributed. Over 60% of cobalt ores are coming from the central african region, which adversely affects the stability of the cobalt supply chain. In addition, the cobalt acid lithium battery has poor thermal stability, so that the cobalt acid lithium battery is generally used in small batteries suitable for consumer electronics, and is difficult to apply to power batteries of new energy automobiles. The ternary positive electrode material (nickel cobalt lithium manganate or nickel cobalt lithium aluminate) partially replaces cobalt elements with nickel, manganese, aluminum and other elements, so that the specific capacity of the material is improved, the cycle life and the thermal stability are improved, and the price of the material is also reduced. Therefore, the ternary battery using the ternary material as the positive electrode can meet the requirements of new energy automobiles in the aspects of battery energy density, service life, safety, battery cost and the like. At present, the ternary battery is widely applied to the power battery of the automobile, and is one of the hot spots which are currently concerned by the battery manufacturing industry.
Although the ternary battery has many advantages, the internal resistance of the battery is rapidly increased during the use process, especially under the condition of high temperature (such as 55 ℃), so that the capacity of the battery is reduced. This increase in internal resistance is mainly due to the breakdown of electrode material particles, the increase in the specific surface area of the electrode, and the increase in the side reaction of electrolyte decomposition, the product of which hinders the transport of lithium ions. On the other hand, an increase in internal resistance in turn causes the battery to generate more heat (joule's law), further exacerbating the deterioration of performance. The method for controlling the increase of the internal resistance of the battery is disclosed to use electrolyte additives (such as CN108923067B and CN106450460A), but the synthesis and purification of the electrolyte additives are difficult, and the mass production is not facilitated. The cost of the additives is also high, increasing the overall cost of the electrolyte and the battery. In addition, electrolyte additives are largely consumed in the early stages of battery cycling, and therefore their positive effects on controlling internal resistance increase over long-term use are limited.
Disclosure of Invention
The invention provides a modified electrode, a preparation method thereof and application thereof in a lithium ion battery. The modified electrode is used in a lithium ion battery, can obviously reduce the internal resistance increasing rate and obviously improve the cycle performance of the battery.
The invention provides a modified electrode in a first aspect, which comprises an electrode and a modification layer on the surface of the electrode; the thickness of the electrode is not higher than 150 μ M, the modification layer contains a composite oxide of lithium and metal M, and the metal M is selected from at least one of Al, Ti, Zr, W, Ta, Hf and the like; the thickness of the modification layer is 25-50 nm.
In the above technical solution, the electrode includes an active material, a conductive material, and a binder. Wherein the mass ratio of the active material to the conductive material to the binder is (60-99): (0.5-40): (0.5-40).
In the above technical scheme, the active material in the electrode is selected from alpha-NaFeO with a crystal structure2Type nickel cobalt lithium manganate (LiNi)xMnyCozO2X + y + z ═ 1) or lithium nickel cobalt aluminate (LiNi)aAlbCocO2And a + b + c is 1). The microstructure of the active material is nano-scale primary particles (excellent)Preferably 2-200 nm) of micro-sized secondary particles (preferably 2-20 microns).
In the above technical solution, the conductive material in the electrode is at least one selected from carbon black, carbon nanotubes, graphene, and conductive graphite.
In the above technical solution, the binder in the electrode is selected from at least one of polyvinylidene fluoride, polytetrafluoroethylene, and polyvinyl alcohol.
In the above technical solution, the thickness of the electrode is not higher than 150 μm, and may be 20-150 μm.
In the technical scheme, the active material particles on the surface of the electrode are provided with cracks, and the width of the cracks is not less than 1nm and can be 1-500 nm.
The second aspect of the present invention provides a method for preparing the modified electrode, comprising:
(1) uniformly mixing an active material, a conductive material and a binder in 1-methyl-2-pyrrolidone, coating the mixed slurry on the surface of an aluminum foil, and drying and rolling to obtain an electrode with an unmodified surface;
(2) performing surface modification on the electrode obtained in the step (1), wherein the surface modification comprises the following steps:
(2.1) preheating step: putting the electrode into a reaction cavity, and heating the electrode by taking hot inert gas as a medium;
(2.2) a deposition step: depositing a modifying layer on the surface of the electrode by adopting an atomic layer deposition method, wherein the atomic layer deposition method comprises the following steps:
(2.2a) introducing the gas-phase precursor of the metal M into a reaction chamber by using a carrier gas in a pulse form;
(2.2b) introducing inert gas for cleaning;
(2.2c) introducing an oxygen source into the reaction cavity by using carrier gas in a pulse mode;
(2.2d) introducing inert gas for cleaning;
the steps (2.2a), (2.2b), (2.2c) and (2.2d) are a deposition period, and after a plurality of deposition periods, the modified electrode intermediate is obtained until the thickness of a certain modification layer is reached;
(3) and (3) heating the modified electrode intermediate obtained in the step (2) at the temperature of 300-500 ℃ for 0.5-2.0h to obtain the modified electrode.
In the above technical solution, in the preheating step, the electrode preheating temperature is 100-.
In the above technical solution, in the deposition step, the pressure of the deposition chamber is not higher than 3 kPa.
In the above technical solution, the inert gas and the carrier are each independently selected from at least one of nitrogen, argon or helium.
In the above technical solution, in the step (2.2a), the gas phase precursor of the metal M is at least one selected from a metal alkyl compound (M-R, M is a metal, R is a methyl OR ethyl group), a metal halide (M-X, M is a metal, X is Cl, Br OR I), OR a metal alkoxide (M-OR, M is a metal, R is an ethyl group, an n-propyl group, an isopropyl group, OR a tert-butyl group), and the pulse time is 0.1 to 10 seconds.
In the above technical solution, in the step (2.2a), the carrier gas is an inert gas, preferably at least one selected from nitrogen, argon, or helium, and the volume fraction of the gas-phase precursor of the metal M in the mixed gas of the carrier gas and the gas-phase precursor of the metal M is not higher than 20%.
In the above technical scheme, in the step (2.2b), an inert gas is introduced for cleaning, wherein the inert gas is at least one selected from nitrogen, argon or helium.
In the above technical scheme, in the step (2.2c), the oxygen source is selected from H2O、O2、H2O2Or O3At least one of (1). The pulse time is 0.1-10 seconds.
In the above technical solution, in the step (2.2c), the carrier gas is an inert gas, preferably at least one selected from nitrogen, argon or helium, and the ratio of the oxygen source in the mixed gas of the carrier gas and the oxygen source is not higher than 20% by volume fraction.
In the above technical scheme, in the step (2.2d), an inert gas is introduced for cleaning, wherein the inert gas is at least one selected from nitrogen, argon or helium.
The invention also provides the application of the modified electrode in a lithium ion battery.
The modified electrode has the following beneficial effects:
1. the modified electrode is characterized in that the surface of the electrode is coated with an electrochemically inert composite oxide modification layer containing lithium and metal M, and the thickness of the electrode and the thickness of the modification layer are controlled, so that the side reaction between active material particles with cracks and electrolyte is reduced, the surface of the electrode is protected, the capacity of the battery can be ensured to be exerted, the internal resistance of the battery is obviously slowed down in the charging and discharging use process, and the capacity retention rate of the battery is obviously increased.
2. The preparation method of the modified electrode is particularly suitable for the electrode prepared by the active material with cracks, and can effectively utilize the reaction of the active material in the electrode and the metal M to form a composite oxide modified layer containing lithium and the metal M while controlling the thickness of the electrode and the thickness of the modified layer, thereby effectively protecting active material particles containing cracks on the surface of the electrode, preventing the growth of the cracks and being beneficial to improving the overall performance of the battery.
Drawings
FIG. 1 is a sectional electron micrograph of active material particles used in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a cross section of a ternary electrode in example 1 of the present invention;
FIG. 3 is a second SEM photograph of a cross-section of a ternary electrode in example 1 of the present invention;
FIG. 4 is a TEM image of the surface of the modified electrode in example 1 of the present invention;
FIG. 5 is a result of X-ray photoelectron spectroscopy of Al element on the surface of the modified electrode in example 1 of the present invention and comparative example 1;
FIG. 6 is the result of X-ray photoelectron spectroscopy Li element on the surface of the modified electrode in example 1 of the present invention;
FIG. 7 shows the analysis results of the depth profile of the surface of the modified electrode in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following specific examples, but it should be understood that these examples are included merely for purposes of illustration and are not intended to limit the invention in any way.
In the invention, the scanning electron microscope photo is a Dutch Phenom Pro scanning electron microscope and is shot under the condition that the accelerating voltage is 5 kV.
In the present invention, the transmission electron microscope photograph was taken under an acceleration voltage of 200kV using a FEI TALOS F200X transmission electron microscope.
In the present invention, the X-ray photoelectron spectrum is measured by an AXIS UltraDLD instrument from Shimadzu-Kratos, Japan.
In the present invention, the thickness of the electrode means the thickness of the electrode at a non-crack portion; the thickness of the modified electrode outer surface modification layer refers to the thickness of the outer surface modification layer at the non-crack position of the electrode.
In the present invention, materials used in experiments and experimental methods are generally described. Although a number of experimental materials and procedures are well known in the art, the invention is described in as much detail as possible.
Example 1
(1) Preparing a ternary positive electrode:
reacting LiNi0.8Co0.10Mn0.10O2Ternary cathode material (the microstructure of the cross section of the particle is shown in figure 1, the micron particle is composed of nanoscale primary particles, alpha-NaFeO2Type), PVDF, conductive carbon black in a ratio of 94.5: 1.5: 4 in the mass ratio of 1-methyl-2-pyrrolidone, coating the mixed slurry on two sides of an aluminum foil, drying and rolling to obtain LiNi0.8Co0.10Mn0.10O2An electrode; the thickness of the electrode measured by a thickness measuring instrument is 60 micrometers (excluding the thickness of the aluminum foil), the scanning electron micrograph of the cross section is shown in fig. 2, the scanning electron micrograph with larger magnification is shown in fig. 3, and from both the micrographs, the active material (namely, LiNi) on the surface of the electrode after the electrode is rolled can be seen0.8Co0.10Mn0.10O2) Cracks in the particles. Cutting off the pole piece with the diameter of 19mm by using a die cutting machine,the surface density of the active material in the electrode is 25.0mg/cm by using a balance weighing mode2。
(2)LiNi0.8Co0.10Mn0.10O2And (3) surface deposition modification of the electrode:
(2.1) preheating step: placing the prepared positive pole piece in an atomic layer deposition reaction cavity, introducing nitrogen with the flow rate of 100 standard liters/minute and the temperature of 200 ℃, preheating the electrode to 150 ℃, continuing to introduce the nitrogen after the temperature is reached, keeping the flow rate of 10 standard liters/minute, keeping the pressure of the deposition reaction cavity at 1.3kPa,
(2.2) a deposition step: depositing a modification layer on the surface of the electrode by adopting an atomic layer deposition method, which comprises the following steps:
(2.2a) introducing trimethylaluminum in a pulse mode for 0.5 second, wherein the carrier gas is nitrogen, and the volume percentage of the trimethylaluminum is 10%; (2.2b) introducing nitrogen gas with the flow rate of 100 standard liters/minute for 10 seconds; (2c) introducing water vapor in a pulse mode for 0.5 second, wherein the carrier gas is nitrogen, and the volume of the water vapor accounts for 10%; (2.2d) introducing nitrogen gas washing with the flow of 100 standard liters/minute for 10 seconds, wherein the 4 steps from (2.2a) to (2.2d) are a modified layer growth period and are repeated for 50 times to obtain a modified electrode intermediate;
(2.3) heating the modified electrode intermediate at 300 ℃ for 1 hour, and cooling to obtain surface LiAlO2Modified LiNi0.8Co0.10Mn0.10O2And an electrode.
The active material (i.e., LiNi) on the surface of the modified electrode can be observed by transmission electron microscopy0.8Co0.10Mn0.10O2) Particle surface modification layer (see fig. 4). By using an X-ray photoelectron spectroscopy test (the detection depth is 10nm), the existence of Al element (figure 5) and Li element (figure 6) on the surface of the modified electrode can be detected, and the modification layer is confirmed to be LiAlO2. The thickness of the modified layer on the surface of the modified electrode was measured to be 30nm by using an argon ion beam etching-X-ray photoelectron spectroscopy method (fig. 7).
(3) Preparing a negative pole piece:
mixing artificial graphite, conductive carbon, CMC, SBR, mixing the raw materials in a weight ratio of 95: 1.8: 1.4: 1.8, uniformly mixing in water, coating the mixed slurry on two sides of a copper foil, drying and rolling to obtain the negative pole piece.
(4) Preparation of lithium ion battery
Preparing the prepared positive pole piece, negative pole piece and Celgard 2325 diaphragm into a soft package battery with the capacity of 1000mAh in a lamination mode, and adding 1.2M LiPF6And (3) charging and discharging EC-DEC-DMC (1: 1: 1 volume ratio) and 1.5 wt% of VC electrolyte for 3 times (4.2-2.7V) by 100mA current to obtain the ternary battery.
(5) And (3) testing the cycle performance:
and carrying out charge-discharge cycle test on the battery at a charge-discharge rate of 1C/1C until the voltage interval is 2.7-4.2V and the test temperature is 55 ℃. 1C is defined as 1000 mA.
(6) Testing internal resistance:
the cells were fully charged at 0.2C, left to stand for 1 hour, and charged at 0.2C (I)1) Discharging for 10s, reading test voltage U1Then 1C (I)2) Discharging for 1s, reading the test voltage U2The DC impedance is obtained by the following formula: rdc＝(U1-U2)/(I2-I1)。
Example 2
(1) Preparation of ternary positive electrode
Reacting LiNi0.8Co0.15Al0.05O2Ternary cathode material (micrometer particles composed of nanoscale primary particles, alpha-NaFeO2Type), PVDF, conductive carbon black in a ratio of 94.5: 1.5: 4 in the mass ratio of 1-methyl-2-pyrrolidone, coating the mixed slurry on two sides of an aluminum foil, drying and rolling to obtain LiNi0.8Co0.15Al0.05O2An electrode; the thickness of the electrode was measured to be 60 μm using a thickness measuring instrument (excluding the thickness of the aluminum foil). Active material of electrode surface (i.e., LiNi)0.8Co0.15Al0.05O2) Cracks in the particles. Cutting off a pole piece with the diameter of 19mm by using a die cutting machine, and weighing by using a balance to obtain the active material in the electrode with the surface density of 25.1mg/cm2。
(2)LiNi0.8Co0.15Al0.05O2And (3) surface deposition modification of the electrode:
(2.1) preheating step: placing the prepared positive pole piece in an atomic layer deposition reaction cavity, introducing nitrogen with the flow rate of 100 standard liters/minute and the temperature of 200 ℃, preheating the electrode to 150 ℃, continuing to introduce the nitrogen after the temperature is reached, keeping the flow rate of 10 standard liters/minute, keeping the pressure of the deposition reaction cavity at 1.3kPa,
(2.2) a deposition step: depositing a modification layer on the surface of the electrode by adopting an atomic layer deposition method, which comprises the following steps:
(2.2a) introducing trimethylaluminum in a pulse mode for 0.5 second, wherein the carrier gas is nitrogen, and the volume percentage of the trimethylaluminum is 10%; (2.2b) introducing nitrogen gas with the flow rate of 100 standard liters/minute for 10 seconds; (2.2c) introducing water vapor in a pulse mode for 0.5 second, wherein the carrier gas is nitrogen, and the volume of the water vapor accounts for 10%; (2.2d) introducing nitrogen gas with the flow rate of 100 standard liters/minute for 10 seconds; the 4 steps from (2.2a) to (2.2d) are a modified layer growth period, and the steps are repeated for 50 times to obtain a modified electrode intermediate;
(2.3) heating the modified electrode intermediate at 400 ℃ for 2 hours, and cooling to obtain LiAlO on the surface2Modified LiNi with a modification layer thickness of 30nm0.8Co0.15Al0.05O2And an electrode.
(3) Preparing a negative pole piece: the same as in example 1.
(4) Preparing a lithium ion battery: a lithium ion battery was produced in the same manner as in example 1 except that the positive electrode in example 1 was replaced with the positive electrode in this example, as compared with example 1.
(5) And (3) testing the cycle performance: the lithium ion battery of this example was tested by the same test method as in example 1.
(6) Testing internal resistance: the lithium ion battery of this example was tested by the same test method as in example 1.
Example 3
(1) Preparing a ternary positive electrode:
this example was prepared as in example 1.
(2)LiNi0.8Co0.10Mn0.10O2And (3) surface deposition modification of the electrode:
(2.1) preheating step: the prepared LiNi0.8Co0.10Mn0.10O2Placing the positive pole piece in an atomic layer deposition reaction cavity, introducing nitrogen with the flow rate of 100 standard liters/minute and the temperature of 200 ℃, preheating the electrode to 150 ℃, continuing to introduce the nitrogen after the temperature is reached, keeping the flow rate of 10 standard liters/minute, keeping the pressure of the deposition reaction cavity at 1.3kPa,
(2.2) a deposition step: depositing a modification layer on the surface of the electrode by adopting an atomic layer deposition method, which comprises the following steps:
(2.2a) introducing tetraisopropyl titanate in a pulse mode for 0.5 seconds, wherein the carrier gas is nitrogen, and the volume percentage of the tetraisopropyl titanate is 10%; (2.2b) introducing nitrogen gas with the flow rate of 100 standard liters/minute for 10 seconds; (2.2c) introducing water vapor in a pulse mode for 0.5 second, wherein the carrier gas is nitrogen, and the volume of the water vapor accounts for 10%; (2.2d) introducing nitrogen gas with the flow rate of 100 standard liters/minute for 10 seconds; the 4 steps from (2.2a) to (2.2d) are a modified layer growth period, and the steps are repeated for 50 times to obtain a modified electrode intermediate;
(2.3) heating the modified electrode intermediate at 300 ℃ for 0.5 hour, and cooling to obtain surface Li2TiO3Modified LiNi with trimming layer thickness of 30nm0.8Co0.10Mn0.10O2And an electrode.
(3) Preparing a negative pole piece: the same as in example 1.
(4) Preparing a lithium ion battery: a lithium ion battery was produced in the same manner as in example 1 except that the positive electrode in example 1 was replaced with the positive electrode in this example, as compared with example 1.
(5) And (3) testing the cycle performance: the lithium ion battery of this example was tested by the same test method as in example 1.
(6) Testing internal resistance: the lithium ion battery of this example was tested by the same test method as in example 1.
Example 4
(1) Preparing a ternary positive electrode:
this example was prepared as in example 1.
(2)LiNi0.8Co0.10Mn0.10O2And (3) surface deposition modification of the electrode:
(2.1) preheating step: the prepared LiNi0.8Co0.10Mn0.10O2Placing the anode piece in an atomic layer deposition reaction cavity, introducing nitrogen with the flow rate of 100 standard liters per minute and the temperature of 200 ℃, preheating the electrode to 150 ℃, continuing to introduce the nitrogen after the temperature is reached, keeping the flow rate of 10 standard liters per minute, keeping the pressure of the deposition reaction cavity at 1.3kPa,
(2.2) a deposition step: depositing a modification layer on the surface of the electrode by adopting an atomic layer deposition method, which comprises the following steps:
(2.2a) introducing zirconium isopropoxide for 1 second in a pulse mode, wherein the carrier gas is nitrogen, and the volume percentage of the zirconium isopropoxide is 10%; (2.2b) introducing nitrogen gas with the flow rate of 100 standard liters/minute for 10 seconds; (2.2c) introducing oxygen in a pulse mode for 1 second, wherein the carrier gas is nitrogen, and the volume of the water vapor accounts for 10%; (2.2d) introducing nitrogen gas with the flow rate of 100 standard liters/minute for 10 seconds; the 4 steps from (2.2a) to (2.2d) are a modified layer growth period, and the steps are repeated for 50 times to obtain a modified electrode intermediate;
(2.3) heating the modified electrode intermediate at 500 ℃ for 0.5 hour, and cooling to obtain surface Li2ZrO3LiNi with modification layer thickness of 30nm0.8Co0.10Mn0.10O2And an electrode.
(3) Preparing a negative pole piece: the same as in example 1.
(4) Preparing a lithium ion battery: a lithium ion battery was produced in the same manner as in example 1 except that the positive electrode in example 1 was replaced with the positive electrode in this example, as compared with example 1.
(5) And (3) testing the cycle performance: the lithium ion battery of this example was tested by the same test method as in example 1.
(6) Testing internal resistance: the lithium ion battery of this example was tested using the same test method as in example 1.
Example 5
(1) Preparing a ternary positive electrode: the same as in example 1.
(2)LiNi0.8Co0.10Mn0.10O2And (3) surface deposition modification of the electrode:
the difference from the embodiment 1 is that: the thickness of the modified layer on the surface of the electrode is 25 nm.
(3) Preparing a negative pole piece: the same as in example 1.
(4) Preparing a lithium ion battery: a lithium ion battery was produced in the same manner as in example 1 except that the positive electrode in example 1 was replaced with the positive electrode in this example, as compared with example 1.
(5) And (3) testing the cycle performance: the lithium ion battery of this example was tested by the same test method as in example 1.
(6) Testing internal resistance: the lithium ion battery of this example was tested by the same test method as in example 1.
Example 6
(1) Preparing a ternary positive electrode: the same as in example 1.
(2)LiNi0.8Co0.10Mn0.10O2And (3) surface deposition modification of the electrode:
the difference from the embodiment 1 is that: the thickness of the modified layer on the surface of the electrode is 35 nm.
(3) Preparing a negative pole piece: the same as in example 1.
(4) Preparing a lithium ion battery: a lithium ion battery was produced in the same manner as in example 1 except that the positive electrode in example 1 was replaced with the positive electrode in this example, as compared with example 1.
(5) And (3) testing the cycle performance: the lithium ion battery of this example was tested by the same test method as in example 1.
(6) Testing internal resistance: the lithium ion battery of this example was tested by the same test method as in example 1.
Example 7
(1) Preparing a ternary positive electrode: the same as in example 1.
(2)LiNi0.8Co0.10Mn0.10O2And (3) surface deposition modification of the electrode:
the difference from the embodiment 1 is that: the thickness of the modified layer on the surface of the electrode is 50 nm.
(3) Preparing a negative pole piece: the same as in example 1.
(4) Preparing a lithium ion battery: a lithium ion battery was produced in the same manner as in example 1 except that the positive electrode in example 1 was replaced with the positive electrode in this example, as compared with example 1.
(5) And (3) testing the cycle performance: the lithium ion battery of this example was tested by the same test method as in example 1.
(6) Testing internal resistance: the lithium ion battery of this example was tested by the same test method as in example 1.
Example 8
(1) Preparing a ternary positive electrode:
reacting LiNi0.8Co0.10Mn0.10O2Ternary positive electrode material (same as example 1), PVDF, conductive carbon black in a ratio of 60: 20: 20 in the weight ratio of 1-methyl-2-pyrrolidone, coating the mixed slurry on two sides of an aluminum foil, drying and rolling to obtain LiNi0.8Co0.10Mn0.10O2An electrode; the thickness of the electrode was measured to be 130 μm (excluding the thickness of the aluminum foil) using a thickness meter. Active material of electrode surface (i.e., LiNi)0.8Co0.10Mn0.10O2) Cracks in the particles. Cutting off the pole piece with the diameter of 19mm by using a die cutter, and weighing by using a balance to obtain the active material in the electrode with the surface density of 24.6mg/cm2。
(2)LiNi0.8Co0.10Mn0.10O2And (3) surface deposition modification of the electrode: the surface of the positive electrode of this example was modified by the same modification method as in example 1.
(3) Preparing a negative pole piece: the same as in example 1.
(4) Preparing a lithium ion battery: a lithium ion battery was produced in the same manner as in example 1 except that the positive electrode in example 1 was replaced with the positive electrode in this example, as compared with example 1.
(5) And (3) testing the cycle performance: the lithium ion battery of this example was tested by the same test method as in example 1.
(6) Testing internal resistance: the lithium ion battery of this example was tested using the same test method as in example 1.
Example 9
(1) Preparing a ternary positive electrode:
reacting LiNi0.8Co0.10Mn0.10O2Ternary positive electrode material (same as example 1), PVDF, conductive carbon black in 96: 2: 2 in the mass ratio of 1-methyl-2-pyrrolidone, coating the mixed slurry on two sides of an aluminum foil, drying and rolling to obtain LiNi0.8Co0.10Mn0.10O2An electrode; the thickness of the electrode was measured to be 58 micrometers (excluding the thickness of the aluminum foil) using a thickness measuring instrument. Active material of electrode surface (i.e., LiNi)0.8Co0.10Mn0.10O2) Cracks in the particles. Cutting off the pole piece with the diameter of 19mm by using a die cutting machine, and weighing by using a balance to obtain the active material in the electrode with the surface density of 25.2mg/cm2。
(2)LiNi0.8Co0.10Mn0.10O2And (3) surface deposition modification of the electrode: the surface of the positive electrode of this example was modified by the same modification method as in example 1.
(3) Preparing a negative pole piece: the same as in example 1.
(4) Preparing a lithium ion battery: a lithium ion battery was produced in the same manner as in example 1 except that the positive electrode in example 1 was replaced with the positive electrode in this example, as compared with example 1.
(5) And (3) testing the cycle performance: the lithium ion battery of this example was tested by the same test method as in example 1.
(6) Testing internal resistance: the lithium ion battery of this example was tested by the same test method as in example 1.
Example 10
(1) Preparing a ternary positive electrode:
reacting LiNi0.8Co0.10Mn0.10O2Ternary positive electrode material (same as example 1), PVDF, conductive carbon black in a weight ratio of 94.5: 1.5: 4 in the mass ratio of 1-methyl-2-pyrrolidone, coating the mixed slurry on two sides of an aluminum foil, drying and rolling to obtain LiNi0.8Co0.10Mn0.10O2An electrode; the thickness of the electrode was measured to be 150 μm using a thickness measuring instrument (excluding the thickness of the aluminum foil). Active material of electrode surface (i.e., LiNi)0.8Co0.10Mn0.10O2) Cracks in the particles. Cutting off the pole piece with the diameter of 19mm by using a die cutter, and weighing by using a balance to obtain the active material in the electrode with the surface density of 33.5mg/cm2。
(2)LiNi0.8Co0.10Mn0.10O2And (3) surface deposition modification of the electrode: the surface of the positive electrode of this example was modified by the same modification method as in example 1.
(3) Preparing a negative pole piece: the same as in example 1.
(4) Preparing a lithium ion battery: a lithium ion battery was produced in the same manner as in example 1 except that the positive electrode in example 1 was replaced with the positive electrode in this example, as compared with example 1.
(5) And (3) testing the cycle performance: the lithium ion battery of this example was tested by the same test method as in example 1.
(6) Testing internal resistance: the lithium ion battery of this example was tested by the same test method as in example 1.
Comparative example 1
(1) Preparing a ternary positive electrode:
reacting LiNi0.8Co0.10Mn0.10O2Ternary positive electrode material (same as example 1), PVDF, conductive carbon black in a weight ratio of 94.5: 1.5: 4, uniformly mixing the mixture in 1-methyl-2-pyrrolidone, coating the mixed slurry on two sides of an aluminum foil, drying and rolling to obtain a ternary positive pole piece; the thickness of the electrode was measured to be 60 μm using a thickness gauge. Cutting off a pole piece with the diameter of 19mm by using a die cutting machine, and obtaining an electrode by using a balance weighing modeThe surface density of the medium active material is 25.0mg/cm2. The presence of Al element on the surface of the material (10 nm depth) cannot be detected by X-ray photoelectron spectroscopy (XPS) test.
(2) Preparing a negative pole piece: the same as in example 1.
(3) Preparing a lithium ion battery: a lithium ion battery was produced in the same manner as in example 1 except that the positive electrode in example 1 was replaced with the positive electrode in this comparative example, as compared with example 1.
(4) And (3) testing the cycle performance: the lithium ion battery of this comparative example was tested by the same test method as in example 1.
(5) Testing internal resistance: the lithium ion battery of this comparative example was tested by the same test method as in example 1.
Comparative example 2
(1) Preparing a ternary positive electrode: the same as in example 1.
(2)LiNi0.8Co0.10Mn0.10O2And (3) surface deposition modification of the electrode:
(2.1) preheating step: the prepared LiNi0.8Mn0.1Co0.1O2Placing the anode piece in an atomic layer deposition reaction cavity, introducing nitrogen with the flow rate of 100 standard liters per minute and the temperature of 200 ℃, preheating the electrode to 150 ℃, continuing to introduce the nitrogen after the temperature is reached, keeping the flow rate of 10 standard liters per minute, keeping the pressure of the deposition reaction cavity at 1.3kPa,
(2.2) a deposition step: depositing a modification layer on the surface of the electrode by adopting an atomic layer deposition method, which comprises the following steps:
(2.2a) introducing trimethylaluminum in a pulse mode for 0.5 second, wherein the carrier gas is nitrogen, and the volume percentage of the trimethylaluminum is 10%; (2.2b) introducing nitrogen gas with the flow rate of 100 standard liters/minute for 10 seconds; (2.2c) introducing water vapor in a pulse mode for 0.5 second, wherein the carrier gas is nitrogen, and the volume of the water vapor accounts for 10%; (2.2d) introducing nitrogen with the flow rate of 100 standard liters/minute for 10 seconds; the 4 steps from (2.2a) to (2.2d) are a modified layer growth period, and the number of times is 8, so that a modified electrode intermediate is obtained;
(2.3) modifying the electrode intermediateHeating the body at 300 ℃ for 1 hour, and cooling to obtain LiAlO on the surface2Modified LiNi with modification layer thickness of 5nm0.8Mn0.1Co0.1O2And an electrode.
(3) Preparing a negative pole piece: the same as in example 1.
(4) Preparing a lithium ion battery: a lithium ion battery was produced in the same manner as in example 1 except that the positive electrode in example 1 was replaced with the positive electrode in the present comparative example as compared with example 1.
(5) And (3) testing the cycle performance: the lithium ion battery of this comparative example was tested by the same test method as in example 1.
(6) Testing internal resistance: the lithium ion battery of this comparative example was tested by the same test method as in example 1.
Comparative example 3
(1) Preparing a ternary positive electrode: the same as in example 1.
(2)LiNi0.8Co0.10Mn0.10O2And (3) surface deposition modification of the electrode:
(2.1) preheating step: the prepared LiNi0.8Mn0.1Co0.1O2Placing the anode piece in an atomic layer deposition reaction cavity, introducing nitrogen with the flow rate of 100 standard liters per minute and the temperature of 200 ℃, preheating the electrode to 150 ℃, continuing to introduce the nitrogen after the temperature is reached, keeping the flow rate of 10 standard liters per minute, keeping the pressure of the deposition reaction cavity at 1.3kPa,
(2.2) a deposition step: depositing a modification layer on the surface of the electrode by adopting an atomic layer deposition method, which comprises the following steps:
(2.2a) introducing trimethylaluminum in a pulse mode for 0.5 second, wherein the carrier gas is nitrogen, and the volume percentage of the trimethylaluminum is 10%; (2.2b) introducing nitrogen gas with the flow rate of 100 standard liters/minute for 10 seconds; (2.2c) introducing water vapor in a pulse mode for 0.5 second, wherein the carrier gas is nitrogen, and the volume of the water vapor accounts for 10%; (2.2d) introducing nitrogen gas with the flow rate of 100 standard liters/minute for 10 seconds; the 4 steps (2.2a) - (2.2d) are a growth cycle of the modified layer, and are repeated for 100 times to obtain a modified electrode intermediate;
(2.3) modification ofHeating the electrode intermediate at 300 ℃ for 1 hour, and cooling to obtain LiAlO on the surface2Modified LiNi with modification layer thickness of 60nm0.8Mn0.1Co0.1O2And an electrode.
(3) Preparing a negative pole piece: the same as in example 1.
(4) Preparing a lithium ion battery: a lithium ion battery was produced in the same manner as in example 1 except that the positive electrode in example 1 was replaced with the positive electrode in this comparative example, as compared with example 1.
(5) And (3) testing the cycle performance: the lithium ion battery of this comparative example was tested by the same test method as in example 1.
(6) Testing internal resistance: the lithium ion battery of this comparative example was tested by the same test method as in example 1.
Comparative example 4
(1) Preparing a ternary positive electrode:
reacting LiNi0.8Co0.10Mn0.10O2Ternary positive electrode material (same as example 1), PVDF, conductive carbon black, 94.5: 1.5: 4 in the mass ratio of 1-methyl-2-pyrrolidone, coating the mixed slurry on two sides of an aluminum foil, drying and rolling to obtain LiNi0.8Co0.10Mn0.10O2An electrode; the thickness of the electrode was measured to be 160 μm (excluding the thickness of the aluminum foil) using a thickness meter. Active material of electrode surface (i.e., LiNi)0.8Co0.10Mn0.10O2) Cracks in the particles. Cutting off the pole piece with the diameter of 19mm by using a die cutting machine, and weighing by using a balance to obtain the active material in the electrode with the surface density of 40.0mg/cm2。
(2)LiNi0.8Co0.10Mn0.10O2And (3) surface deposition modification of the electrode: the positive electrode of this comparative example was surface-modified by the same modification method as in example 1.
(3) Preparing a negative pole piece: the same as in example 1.
(4) Preparing a lithium ion battery: a lithium ion battery was produced in the same manner as in example 1 except that the positive electrode in example 1 was replaced with the positive electrode in this comparative example, as compared with example 1.
(5) And (3) testing the cycle performance: the lithium ion battery of this comparative example was tested by the same test method as in example 1.
(6) Testing internal resistance: the lithium ion battery of this comparative example was tested by the same test method as in example 1.
Comparative example 5
(1) Preparing a ternary positive electrode:
reacting LiNi0.8Co0.10Mn0.10O2Ternary positive electrode material (same as example 1), PVDF, conductive carbon black in a weight ratio of 94.5: 1.5: 4, uniformly mixing the mixture in 1-methyl-2-pyrrolidone, coating the mixed slurry on two sides of an aluminum foil, and drying to obtain the ternary positive electrode plate without broken active material particles (the electrode is not rolled, so the active material particles in the electrode are not broken and do not contain cracks). The thickness of the electrode was measured to be 100 μm using a thickness gauge. Cutting off the pole piece with the diameter of 19mm by using a die cutting machine, and weighing by using a balance to obtain the active material in the electrode with the surface density of 25.0mg/cm2。
(2)LiNi0.8Co0.10Mn0.10O2And (3) surface deposition modification of the electrode: the positive electrode of this comparative example was surface-modified by the same modification method as in example 1.
(3) Preparing a negative pole piece: the same as in example 1.
(4) Preparing a lithium ion battery: a lithium ion battery was produced in the same manner as in example 1 except that the positive electrode in example 1 was replaced with the positive electrode in this comparative example, as compared with example 1.
(5) And (3) testing the cycle performance: the lithium ion battery of this comparative example was tested by the same test method as in example 1.
(6) Testing internal resistance: the lithium ion battery of this comparative example was tested by the same test method as in example 1.
Comparative example 6
(1) Preparing a ternary positive electrode:
reacting LiNi0.8Co0.10Mn0.10O2Ternary positive electrode materialMaterial (the microstructure of the cross section of the particle is shown in figure 1, the micron particle is composed of nanoscale primary particles, alpha-NaFeO2Type), PVDF, conductive carbon black in a ratio of 94.5: 1.5: 4 in the mass ratio of 1-methyl-2-pyrrolidone, coating the mixed slurry on two sides of an aluminum foil, drying and rolling to obtain LiNi0.8Co0.10Mn0.10O2An electrode; the thickness of the electrode measured by the thickness measuring instrument was 60 μm (excluding the thickness of the aluminum foil), the scanning electron micrograph of the cross section was shown in FIG. 2, and the scanning electron micrograph with a larger magnification was shown in FIG. 3, both of which show that the active material (i.e., LiNi) on the surface of the electrode after the electrode was rolled0.8Co0.10Mn0.10O2) Cracks in the particles. Cutting off the pole piece with the diameter of 19mm by using a die cutting machine, and weighing by using a balance to obtain the active material in the electrode with the surface density of 25.0mg/cm2。
(2)LiNi0.8Co0.10Mn0.10O2And (3) surface deposition modification of the electrode:
(2.1) preheating step: placing the prepared positive pole piece in an atomic layer deposition reaction cavity, introducing nitrogen with the flow rate of 100 standard liters/minute and the temperature of 200 ℃, preheating the electrode to 150 ℃, continuing to introduce the nitrogen after the temperature is reached, keeping the flow rate of 10 standard liters/minute, keeping the pressure of the deposition reaction cavity at 1.3kPa,
(2.2) a deposition step: depositing a modification layer on the surface of the electrode by adopting an atomic layer deposition method, which comprises the following steps:
(2.2a) introducing trimethylaluminum in a pulse mode for 0.5 second, wherein the carrier gas is nitrogen, and the volume of the trimethylaluminum accounts for 10%; (2.2b) introducing nitrogen gas with the flow rate of 100 standard liters/minute for 10 seconds; (2c) introducing water vapor in a pulse mode for 0.5 second, wherein the carrier gas is nitrogen, and the volume of the water vapor accounts for 10%; (2.2d) introducing nitrogen gas washing with the flow of 100 standard liters/minute for 10 seconds, wherein the 4 steps from (2.2a) to (2.2d) are a modified layer growth period and are repeated for 50 times to obtain a modified electrode intermediate;
(2.3) direct cooling to obtain Al on the surface2O3Modified LiNi0.8Co0.10Mn0.10O2And an electrode.
(3) Preparing a negative pole piece:
mixing artificial graphite, conductive carbon, CMC, SBR, mixing the raw materials in a weight ratio of 95: 1.8: 1.4: and 1.8, uniformly mixing the mixture in water, coating the mixed slurry on two sides of a copper foil, and drying and rolling to obtain the negative pole piece.
(4) Preparation of lithium ion battery
Preparing the prepared positive pole piece, negative pole piece and Celgard 2325 diaphragm into a soft package battery with the capacity of 1000mAh in a lamination mode, and adding 1.2M LiPF6And (3) charging and discharging EC-DEC-DMC (1: 1: 1 volume ratio) and 1.5 wt% of VC electrolyte for 3 times (4.2-2.7V) by 100mA current to obtain the ternary battery.
(5) And (3) testing the cycle performance:
and carrying out charge-discharge cycle test on the battery at a charge-discharge rate of 1C/1C until the voltage interval is 2.7-4.2V and the test temperature is 55 ℃. 1C is defined as 1000 mA.
(6) Testing internal resistance:
the cell was fully charged at 0.2C, left for 1 hour, and then charged at 0.2C (I)1) Discharging for 10s, reading test voltage U1Then with 1C (I)2) Discharging for 1s, reading the test voltage U2The DC impedance is obtained by the following formula: r isdc＝(U1-U2)/(I2-I1)。
TABLE 1 Performance test results for each example cell
As can be seen from the test results in table 1, compared with comparative examples 1 to 6, the method of using modification on the electrode surface according to the present invention can effectively and significantly slow down the increase of internal resistance of the battery, and can also obtain significantly better capacity retention rate of the battery.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A modified electrode comprises an electrode and a modification layer on the surface of the electrode; the thickness of the electrode is not higher than 150 micrometers; the modification layer contains a composite oxide of lithium and metal M, and the metal M is selected from at least one of Al, Ti, Zr, W, Ta and Hf; the thickness of the modification layer is 25-50 nm.
2. The modified electrode of claim 1, wherein the electrode comprises an active material, a conductive material, and a binder; wherein the mass ratio of the active material to the conductive material to the binder is (60-99): 0.5-40): (0.5-40).
3. The modified electrode of claim 2, wherein the active material in the electrode is selected from the group consisting of alpha-NaFeO having a crystal structure2At least one of nickel cobalt lithium manganate or nickel cobalt lithium aluminate in a form of a micro-structure, wherein the micro-structure of the active material is a micro-scale secondary particle composed of nano-scale primary particles;
and/or the conductive material in the electrode is selected from at least one of carbon black, carbon nano tube, graphene, conductive graphite and conductive high polymer material;
and/or the binder in the electrode is selected from at least one of polyvinylidene fluoride, polytetrafluoroethylene and polyvinyl alcohol.
4. The modified electrode according to claim 1 or 3, wherein the active material particles on the surface of the electrode have cracks of not less than 1 nm.
5. The modified electrode of any of claims 1-4, wherein the thickness of the electrode is 20-150 microns.
6. A method of making a modified electrode according to any one of claims 1 to 5, comprising:
(1) uniformly mixing the electrode in 1-methyl-2-pyrrolidone, coating the mixed slurry on the surface of an aluminum foil, and drying and rolling to obtain an electrode with an unmodified surface;
(2) performing surface modification on the electrode obtained in the step (1), wherein the surface modification comprises the following steps:
(2.1) preheating step: putting the electrode into a reaction cavity, and heating the electrode by taking hot inert gas as a medium;
(2.2) a deposition step: depositing a modification layer on the surface of the electrode by using an atomic layer deposition method, comprising:
(2.2a) introducing the gas-phase precursor of the metal M into a reaction chamber by using a carrier gas in a pulse form;
(2.2b) introducing inert gas for cleaning;
(2.2c) introducing an oxygen source into the reaction cavity by using carrier gas in a pulse mode;
(2.2d) introducing inert gas for cleaning;
the steps (2.2a), (2.2b), (2.2c) and (2.2d) are a deposition period, and after a plurality of deposition periods, the modified electrode intermediate is obtained until the thickness of a certain modification layer is reached;
(3) heating the modified electrode intermediate obtained in the step (2) at the temperature of 300-500 ℃ for 0.5-2.0h to obtain the modified electrode.
7. The method according to claim 6, wherein in the preheating step, the electrode preheating temperature is 100-200 ℃, and the inert gas used for preheating is at least one selected from nitrogen, argon and helium.
8. The production method according to claim 6, wherein in the deposition step, the pressure of the deposition chamber is not higher than 3 kPa.
9. The production method according to claim 6, wherein in the step (2.2a), the gas-phase precursor of the metal M is at least one selected from the group consisting of a metal alkyl compound, a metal halide, or a metal alkoxide, and the pulse time is 0.1 to 10 seconds; the volume fraction of the gas-phase precursor of the metal M accounts for not more than 20% of the gas mixture of the carrier gas and the gas-phase precursor of the metal M;
and/or, the inert gas and the carrier are each independently selected from at least one of nitrogen, argon or helium;
and/or, in step (2c), the oxygen source is selected from H2O、O2、H2O2Or O3At least one of them, the pulse time is 0.1-10 seconds; the proportion of the oxygen source to the oxygen source in the mixed gas of the carrier gas and the oxygen source is not higher than 20% by volume fraction.
10. Use of the modified electrode according to any one of claims 1 to 5 or the modified electrode prepared by the preparation method according to any one of claims 6 to 9 in a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011506787.0A CN114649531A (en) | 2020-12-18 | 2020-12-18 | Modified electrode and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011506787.0A CN114649531A (en) | 2020-12-18 | 2020-12-18 | Modified electrode and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114649531A true CN114649531A (en) | 2022-06-21 |
Family
ID=81991484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011506787.0A Pending CN114649531A (en) | 2020-12-18 | 2020-12-18 | Modified electrode and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114649531A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024103492A1 (en) * | 2022-11-14 | 2024-05-23 | 深圳市原速光电科技有限公司 | Lithium ion battery and positive electrode sheet thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040023106A1 (en) * | 2002-08-02 | 2004-02-05 | Benson Martin H. | Apparatus and method for fracture absorption layer |
| CN103022415A (en) * | 2011-09-26 | 2013-04-03 | 比亚迪股份有限公司 | Positive pole, preparation method thereof and lithium-ion battery |
| US20150325877A1 (en) * | 2012-06-29 | 2015-11-12 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | A battery of lithium-ion type with a cathode of varying porosity, and a corresponding method |
| KR20160090580A (en) * | 2015-01-22 | 2016-08-01 | 삼성에스디아이 주식회사 | Positive electrode active material, preparing method thereof, and lithium secondary battery employing positive electrode comprising the positive electrode active material |
| CN107706351A (en) * | 2017-09-30 | 2018-02-16 | 深圳市贝特瑞纳米科技有限公司 | A kind of positive plate, preparation method and include its lithium ion battery |
| CN108365181A (en) * | 2017-11-23 | 2018-08-03 | 山东省科学院能源研究所 | A kind of nickelic layered cathode material method of modifying |
| CN108565453A (en) * | 2018-04-04 | 2018-09-21 | 格林美（无锡）能源材料有限公司 | A kind of positive electrode and preparation method thereof that surface is modified |
| JP2018206669A (en) * | 2017-06-07 | 2018-12-27 | Ｄｏｗａエレクトロニクス株式会社 | Positive electrode active material powder and manufacturing method thereof, and all-solid type lithium secondary battery |
| CN110993887A (en) * | 2019-12-31 | 2020-04-10 | 恩创动力设备(南京)有限公司 | Preparation method of metal oxide coated lithium ion battery anode |
| US20200152976A1 (en) * | 2017-05-31 | 2020-05-14 | The Board Of Trustees Of The Leland Stanford Junior University | Atomic layer deposition of stable lithium ion conductive interfacial layer for stable cathode cycling |
| CN111477867A (en) * | 2020-05-21 | 2020-07-31 | 苏州大学 | Modification method of high-nickel ternary cathode material of lithium ion battery |
-
2020
- 2020-12-18 CN CN202011506787.0A patent/CN114649531A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040023106A1 (en) * | 2002-08-02 | 2004-02-05 | Benson Martin H. | Apparatus and method for fracture absorption layer |
| CN103022415A (en) * | 2011-09-26 | 2013-04-03 | 比亚迪股份有限公司 | Positive pole, preparation method thereof and lithium-ion battery |
| US20150325877A1 (en) * | 2012-06-29 | 2015-11-12 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | A battery of lithium-ion type with a cathode of varying porosity, and a corresponding method |
| KR20160090580A (en) * | 2015-01-22 | 2016-08-01 | 삼성에스디아이 주식회사 | Positive electrode active material, preparing method thereof, and lithium secondary battery employing positive electrode comprising the positive electrode active material |
| US20200152976A1 (en) * | 2017-05-31 | 2020-05-14 | The Board Of Trustees Of The Leland Stanford Junior University | Atomic layer deposition of stable lithium ion conductive interfacial layer for stable cathode cycling |
| JP2018206669A (en) * | 2017-06-07 | 2018-12-27 | Ｄｏｗａエレクトロニクス株式会社 | Positive electrode active material powder and manufacturing method thereof, and all-solid type lithium secondary battery |
| CN107706351A (en) * | 2017-09-30 | 2018-02-16 | 深圳市贝特瑞纳米科技有限公司 | A kind of positive plate, preparation method and include its lithium ion battery |
| CN108365181A (en) * | 2017-11-23 | 2018-08-03 | 山东省科学院能源研究所 | A kind of nickelic layered cathode material method of modifying |
| CN108565453A (en) * | 2018-04-04 | 2018-09-21 | 格林美（无锡）能源材料有限公司 | A kind of positive electrode and preparation method thereof that surface is modified |
| CN110993887A (en) * | 2019-12-31 | 2020-04-10 | 恩创动力设备(南京)有限公司 | Preparation method of metal oxide coated lithium ion battery anode |
| CN111477867A (en) * | 2020-05-21 | 2020-07-31 | 苏州大学 | Modification method of high-nickel ternary cathode material of lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| JIN XIE，ET AL.: ""Engineering the surface of LiCoO2 electrodes using atomic layer deposition for stable high-voltage lithium ion batteries "", NANO RESEARCH, vol. 10, no. 11, pages 3754 - 3764, XP036342105, DOI: 10.1007/s12274-017-1588-1 * |
| 连芳 主编: "《电化学储能器件及关键材料》", 31 July 2019, 北京：冶金工业出版社, pages: 89 - 91 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024103492A1 (en) * | 2022-11-14 | 2024-05-23 | 深圳市原速光电科技有限公司 | Lithium ion battery and positive electrode sheet thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7352727B2 (en) | Nickel lithium manganate composite material, manufacturing method thereof and lithium ion battery | |
| US9774033B2 (en) | Process for producing silicon nanowires directly from silicon particles | |
| TWI393287B (en) | A fiber electrode for a lithium secondary battery, a method for manufacturing the same, and a lithium secondary battery having a fiber electrode | |
| JP2022550265A (en) | Cobalt-free positive electrode material, manufacturing method thereof, and lithium ion battery | |
| Xiong et al. | Three-dimensional porous nano-Ni/Fe 3 O 4 composite film: Enhanced electrochemical performance for lithium-ion batteries | |
| JP5079951B2 (en) | Non-aqueous electrolyte secondary battery positive electrode active material, its manufacturing method, non-aqueous electrolyte secondary battery, and positive electrode manufacturing method | |
| WO2018024184A1 (en) | Method for preparing germanium/graphene/titanium dioxide nanofiber composite material, and battery | |
| CN106252651B (en) | A kind of porous composite negative pole material of lithium ion battery and preparation method thereof | |
| CN107437617B (en) | A kind of surface modification method, gained richness lithium material and application improving rich lithium material chemical property | |
| KR20120010211A (en) | Porous silicon based alloy, method of preparing the same, and negative active material for rechargeable lithium battery and rechargeable lithium battery including the same | |
| WO2022199389A1 (en) | Silicon-oxygen composite negative electrode material, preparation method therefor, and lithium ion battery | |
| CN108807928B (en) | Synthesis of metal oxide and lithium ion battery | |
| CN109524649B (en) | Sodium-ion battery positive electrode material with coating structure and preparation method and application thereof | |
| CN103840176B (en) | Three-dimensional grapheme based combined electrode of a kind of area load Au nano particle and its preparation method and application | |
| CN112467122B (en) | Lithium orthosilicate composite material and preparation method and application thereof | |
| CN108306009A (en) | A kind of silicon-carbon oxide composite negative pole material, preparation method and lithium ion battery | |
| CN107112519A (en) | Cathode active material, its preparation method and the lithium secondary battery for including the material | |
| CN115064700A (en) | Negative current collector of non-negative lithium metal battery and preparation method and application thereof | |
| CN113264519A (en) | Modified carbon nanotube and preparation method thereof, negative electrode material, negative electrode plate and lithium ion battery | |
| Hou et al. | Recent development of low temperature plasma technology for lithium-ion battery materials | |
| CN108598462B (en) | Sodium-ion battery negative electrode material and preparation method and application thereof | |
| CN111029541B (en) | Silicon-carbon composite electrode material for honeycomb-like lithium ion battery and preparation method thereof | |
| CN114649531A (en) | Modified electrode and preparation method and application thereof | |
| Liu et al. | Synthesis of FeO-nanowires/NiCo2O4-nanosheets core/shell heterostructure as free-standing electrode with enhanced lithium storage properties | |
| KR20130016629A (en) | Metal-air cell, preparing method of the same, and cell module containing the same |
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 |