CN117543008B - Nano rod-shaped lithium nickel manganese oxide positive electrode material, preparation method and battery - Google Patents
Nano rod-shaped lithium nickel manganese oxide positive electrode material, preparation method and battery Download PDFInfo
- Publication number
- CN117543008B CN117543008B CN202410034490.0A CN202410034490A CN117543008B CN 117543008 B CN117543008 B CN 117543008B CN 202410034490 A CN202410034490 A CN 202410034490A CN 117543008 B CN117543008 B CN 117543008B
- Authority
- CN
- China
- Prior art keywords
- manganese oxide
- positive electrode
- electrode material
- lithium nickel
- nickel manganese
- 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.)
- Active
Links
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 28
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 3
- 239000011029 spinel Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 239000010405 anode material Substances 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 11
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 6
- 239000002073 nanorod Substances 0.000 claims description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 16
- 238000001816 cooling Methods 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010277 constant-current charging Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005303 weighing Methods 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
- H01M4/48—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- 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
- 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)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of batteries, and discloses a nano rod-shaped lithium nickel manganese oxide positive electrode material, a preparation method and a battery, wherein the positive electrode material is of a spinel structure, is rod-shaped, and has a length of 500nm-1 mu m and a diameter of 60-100nm. The invention can prepare the nano rod-shaped manganese oxide precursor materials with consistent morphology and size in batches through a simple preparation process, and the lithium nickel manganese oxide finished product material synthesized by the precursor has obviously improved electrochemical performance, and particularly has greatly improved rate capability compared with the material synthesized by the existing solid phase method. The invention also provides a lithium ion soft-packed full battery assembled by the lithium nickel manganese oxide positive electrode material prepared by the preparation method, and the battery has excellent first charge and discharge performance, rate capability and cycle performance.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a nano rod-shaped lithium nickel manganese oxide positive electrode material, a preparation method and a battery.
Background
Lithium nickel manganate (LiNi) 0.5 Mn 1.5 O 4 ) The positive electrode material is prepared from lithium manganate (LiMn) 2 O 4 ) Positive electrode material doped with Ni 2+ The lithium battery anode material has the characteristics of high working voltage platform of about 4.7V, excellent multiplying power performance, no noble metal element, low cost, good thermal stability, higher energy density than the traditional anode material and the like, and is expected to become the next-generation lithium battery anode material.
However, when the lithium nickel manganese oxide positive electrode is subjected to lithium removal, a two-phase reaction is contained, so that the kinetics of the lithium removal reaction is slow, and the rate capability of the lithium nickel manganese oxide material is reduced. Second, the interface due to the high voltage characteristics reacts strongly with the electrolyte, resulting in severe capacity fade at high rates.
At present, common methods for improving the multiplying power performance of the lithium nickel manganese oxide positive electrode material comprise element doping, surface coating and morphology regulation. Through changing experimental conditions and regulating and controlling the morphology of the material, the structure of the material can be more stable, the intercalation/deintercalation of lithium ions can be accelerated, and the aim of improving the electrochemical performance of the material can be achieved. The nanocrystallization material can shorten the diffusion path of lithium ions, improve the transmission rate of the lithium ions, and further improve the rate capability and the cycle capability of the electrode material.
The existing synthesis methods (coprecipitation method, hydrothermal method and the like) of the nano lithium manganate material are too strict in synthesis conditions, high-pressure reaction kettles and various organic solvents are needed, the steps are complex, the cost is too high, and the method is not suitable for batch preparation and industrial production.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, does not use a high-pressure reaction kettle and various organic solvents, simplifies a material synthesis route, and provides a lithium nickel manganese oxide positive electrode material, a preparation method thereof and a lithium ion battery.
The technical scheme for realizing the purpose of the invention is as follows:
the first aspect of the invention provides a nano rod-shaped lithium nickel manganese oxide anode material which has a spinel structure, a rod shape, a rod length of 500nm-1 mu m and a diameter of 60-100nm, and has a rough surface, uniform morphology and uniform size.
The second aspect of the invention is a preparation method of the nano rod-shaped lithium nickel manganese oxide positive electrode material, which comprises the following steps:
s1, according to a mole ratio of 1:1, dissolving a manganese source and sodium persulfate in deionized water, wherein the concentration of manganese ions is 0.1-0.4mol/L, injecting the mixed solution into a reaction kettle for reflux reaction, wherein the reaction temperature is 100-120 ℃, the heat preservation time is 12-15 hours, the mechanical stirring speed is 100-200 rmp, and filtering, washing and drying steps are performed after the reaction is finished to recover a precipitate product; sintering the dried precipitate product at 500-550 ℃ for 4-6 hours to obtain a nanometer manganese oxide precursor;
s2, mixing the nano manganese oxide precursor with a nickel source and a lithium source according to a molar ratio Mn of Ni:Li=1.5-1.6: 0.5: and (3) uniformly mixing 1-1.2, and sintering at 650-750 ℃ for 18-24 hours in an air atmosphere to obtain the nano rod-shaped lithium nickel manganese oxide anode material.
Further, the manganese source is one or more than two of manganese sulfate, manganese acetate and manganese carbonate.
Further, the temperature rising rate of the S1 to the sintering temperature is 2.5 ℃/min to 3.5 ℃/min.
Further, the lithium source is one or more than two of lithium carbonate, lithium hydroxide and lithium acetate.
Further, the nickel source is one or more of nickel acetate, nickel nitrate and nickel hydroxide.
The third aspect of the invention provides a lithium ion soft package battery, which uses the nanorod-shaped lithium nickel manganese oxide positive electrode material.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the coprecipitation method used for preparing the nickel-manganese precursor in the prior art, the method does not need to use acid or alkali to regulate and control the PH value, has simpler preparation process, lower requirements on equipment and lower synthesis cost;
2. according to the preparation method of the nanometer manganese oxide precursor, provided by the invention, one-dimensional nanometer rod-shaped materials with uniform morphology and size can be prepared in batches without high-temperature and high-pressure conditions;
3. after preparing the precursor, mixing the precursor with a lithium source and a nickel source by a solid phase method, and performing heat treatment to obtain a lithium nickel manganese oxide positive electrode material, wherein the positive electrode material has a nanorod shape similar to the precursor, and the one-dimensional nanotopography provides a rapid lithium ion transmission channel, so that the rate capability of the lithium nickel manganese oxide positive electrode material is remarkably improved compared with a material prepared by a common solid phase method;
4. the preparation method of the nano rod-shaped lithium nickel manganese oxide anode material has the advantages of simple preparation process, high production efficiency, environmental protection, easy mass production and the like, and can be used in industrial production;
5. the lithium nickel manganese oxide anode material prepared by the method has excellent performances in the aspects of capacity, multiplying power, cycle performance and the like;
6. the invention provides a soft-package full battery assembled by the nano rod-shaped lithium nickel manganese oxide positive electrode material obtained by the preparation method, and the full battery shows excellent electrochemical performance, which proves the great potential of the lithium nickel manganese oxide positive electrode material obtained by the preparation method in commercial application.
Drawings
FIG. 1 is an XRD pattern of a nano manganese sesquioxide precursor prepared in example 1;
FIG. 2 is an SEM image of a nano manganese trioxide precursor prepared according to example 1;
FIG. 3 is an XRD pattern of the lithium nickel manganese oxide positive electrode material prepared in example 1;
FIG. 4 is an SEM image of a lithium nickel manganese oxide positive electrode material prepared in example 1;
fig. 5 is a charge-discharge curve diagram of button half-cells prepared from the lithium nickel manganese oxide cathode material of example 1 at different rates;
FIG. 6 is a graph of the rate performance of a button cell half-cell made from the lithium nickel manganese oxide positive electrode material of example 1;
FIG. 7 is a graph showing the cycle of a button cell half cell prepared from the lithium nickel manganese oxide cathode material of example 1 at a 5C rate;
FIG. 8 is a graph of the rate capability of a lithium nickel manganese oxide/graphite pouch cell prepared from the lithium nickel manganese oxide positive electrode material of example 1;
FIG. 9 is an SEM image of a nano manganese sesquioxide precursor prepared according to comparative example 1;
FIG. 10 is an SEM image of a nano manganese sesquioxide precursor prepared according to comparative example 2;
FIG. 11 is an SEM image of a nano manganese sesquioxide precursor prepared according to comparative example 3;
fig. 12 is an SEM image of the lithium nickel manganese oxide cathode material prepared in comparative example 4.
Detailed Description
The present invention will be further illustrated by the accompanying drawings and specific examples which are given by way of illustration only and should not be construed to limit the scope of the invention, nor the invention.
Example 1
The preparation method of the nano rod-shaped lithium nickel manganese oxide positive electrode material comprises the following steps:
step 1: dissolving 4.28mol of manganese sulfate and 4.28mol of sodium persulfate in 21L of deionized water, injecting into a glass reaction kettle, stirring and heating at 100-200 rmp, and continuing reflux reaction for 12 hours at the temperature after the system temperature is stabilized at 100 ℃; and after the reaction is finished, naturally cooling to room temperature, taking out a precipitate in the reaction kettle, washing and filtering for multiple times, drying, placing the precipitate in a muffle furnace, sintering at 550 ℃ for 4 hours, and naturally cooling to room temperature to obtain the nano manganese sesquioxide precursor.
FIG. 1 is an XRD image of a nano manganese sesquioxide precursor, and FIG. 2 is an SEM image of the nano manganese sesquioxide precursor, showing a nanorod shape with a length of 1-1.5 μm and a diameter of 60-100nm.
Step 2: fully mixing a nano manganese sesquioxide precursor with nickel acetate and lithium acetate, wherein the molar ratio Mn of the three is that Ni is that Li=1.5: 0.5:1.05, placing the material in a muffle furnace, wherein the heating rate is 2.5 ℃/min-3.5 ℃/min, sintering the material for 24 hours at 700 ℃ in an air atmosphere, and naturally cooling the material to room temperature to obtain the high-rate lithium nickel manganese oxide anode material.
Fig. 3 is an XRD image of the lithium nickel manganese oxide positive electrode material, fig. 4 is an SEM image of the lithium nickel manganese oxide positive electrode material, the nanorod shape of the precursor is well preserved, the nanorod length is 500nm-1 μm, the diameter is 60-100nm, the surface of the nanorod is rough, and the shape and the size are uniform.
The lithium nickel manganese oxide cathode material prepared in example 1, conductive carbon black (Super-P), polyvinylidene fluoride (PVDF) were mixed in an amount of 7:2:1, and sufficiently dispersing the mixture by using N-methylpyrrolidone (NMP) as a solvent. And (3) coating the prepared anode slurry on one side of an aluminum foil, punching and weighing after drying, and then assembling a CR2032 button cell by taking a metal lithium sheet as a negative electrode, and performing charge and discharge test on a blue cell test system. The voltage range is: 3.0V to 5.0V. The charge and discharge capacities of the resulting button cells were measured at 1, 2, 5, 10, 20 and 30C, and then the capacity retention rates were measured after cycling at 5C for 800 cycles.
The discharge capacities at 1, 2, 5, 10, 20 and 30C rates were 137.3, 131.9, 116.6, 91.3, 66.5 and 29.7mAh/g, respectively, and the capacity retention rate was 80% after 800 cycles at 5C rate.
Fig. 5 is a charge-discharge curve diagram of the lithium nickel manganese oxide button half cell at different multiplying powers, fig. 6 is a multiplying power performance diagram of the lithium nickel manganese oxide button half cell, and fig. 7 is a cycle curve diagram of the lithium nickel manganese oxide button half cell at 5C multiplying power.
Soft package full cell preparation and testing: mixing a lithium nickel manganese oxide positive electrode material, a polyvinylidene fluoride (PVDF) binder and conductive carbon black in a mass ratio of 91:4:5, and fully dispersing by taking N-methylpyrrolidone (NMP) as a solvent. Coating the prepared positive electrode slurry on aluminum foil with a surface loading of 35.18mg/cm 2 And drying, rolling, cutting and the like to obtain the positive plate. Artificial graphite, sodium carboxymethyl cellulose (CMC), conductive carbon black, styrene Butadiene Rubber (SBR) were mixed at a ratio of 95:1:1.5: mixing is carried out according to the mass ratio of 2.5,and water is used as a solvent for full dispersion. Coating the obtained cathode slurry on copper foil with a surface load of 13.81mg/cm 2 And drying, rolling, cutting and the like to obtain the negative plate. And (3) laminating the positive plate, the diaphragm and the negative plate, and packaging into an aluminum plastic bag to obtain the standby lithium nickel manganese oxide/graphite battery. LiPF at 1.15mol/L in an argon glove box 6 [ Ethylene Carbonate (EC) +dimethyl carbonate (DMC) +ethylmethyl carbonate (EMC) ] wherein the volume ratio of EC: DMC: EMC is=1:2:2, electrolyte is injected into a lithium nickel manganese oxide/graphite soft-pack battery (nominal capacity is 805 mAh), standing is carried out for 48h after sealing, then the battery is formed on a blue charge-discharge tester, the voltage range is 3.5V-5.0V, and the formation conditions are that: (1) 0.05C constant current charging for 3h; (2) 0.1C constant current charging for 3h; (3) 0.15C constant current charging for 3h; (4) 0.2C constant current charging to 5V; and (5) vacuum-exhausting and sealing.
And (3) multiplying power performance test: and (3) carrying out multiplying power charge and discharge (3-5V) on the battery after formation at 25 ℃ in a blue charge and discharge tester at 0.5C, 1C, 2C and 5C respectively.
The discharge capacities at 0.5C, 1C, 2C and 5C are 674.4, 653.4, 539.9 and 444.1mAh respectively, and FIG. 8 is a graph of the rate performance of a lithium nickel manganese oxide/graphite soft-pack battery.
Example 2
The preparation method of the nano rod-shaped lithium nickel manganese oxide positive electrode material comprises the following steps:
step 1: dissolving 4.28mol of manganese carbonate and 4.28mol of sodium persulfate in 21L of deionized water, injecting into a glass reaction kettle, stirring and heating at 100-200 rmp, and continuing reflux reaction for 12 hours at the temperature after the system temperature is stabilized at 100 ℃; and after the reaction is finished, naturally cooling to room temperature, taking out a precipitate in the reaction kettle, washing and filtering for multiple times, drying, placing the precipitate in a muffle furnace, preserving heat for 4 hours at 550 ℃, and naturally cooling to room temperature to obtain the nano manganese sesquioxide precursor.
Step 2: fully mixing the precursor with nickel hydroxide and lithium carbonate, wherein the mole ratio Mn of the three is Ni: 0.5:1.05, placing the lithium nickel manganese oxide anode material into a muffle furnace, preserving heat for 24 hours at 700 ℃ in an air atmosphere, and naturally cooling to room temperature to obtain the high-rate lithium nickel manganese oxide anode material.
Example 3
The preparation method of the nano rod-shaped lithium nickel manganese oxide positive electrode material comprises the following steps:
step 1: dissolving 4.28mol of manganese acetate and 4.28mol of sodium persulfate in 21L of deionized water, injecting into a glass reaction kettle, stirring and heating at 100-200 rmp, and continuing reflux reaction for 12 hours at the temperature after the system temperature is stabilized at 100 ℃; and after the reaction is finished, naturally cooling to room temperature, taking out a precipitate in the reaction kettle, washing and filtering for multiple times, drying, placing the precipitate in a muffle furnace, preserving heat for 6 hours at 550 ℃, and naturally cooling to room temperature to obtain the nano manganese sesquioxide precursor.
Step 2: fully mixing the precursor with nickel nitrate and lithium hydroxide, wherein the mol ratio Mn of the precursor to the lithium hydroxide is Ni: 0.5:1.05, placing the lithium nickel manganese oxide anode material into a muffle furnace, preserving heat for 24 hours at 700 ℃ in an air atmosphere, and naturally cooling to room temperature to obtain the high-rate lithium nickel manganese oxide anode material.
Example 4
The difference from example 1 is that the reaction temperature of the reflux reaction in step 1 was 120 ℃.
Example 5
The difference from example 1 is that in step 2, the sintering time in the muffle furnace is 18 hours.
Example 6
The difference from example 1 is that in step 2, the Mn to Ni to Li molar ratio is 1.5:0.5:1.1.
the lithium ion button cell batteries were assembled in the same manner as in example 1 and were subjected to charge and discharge tests at 1C, 2C, 5C, and 10C magnifications, and the rate discharge capacity data of examples 1 to 6 are shown in table 1, which shows excellent rate performance.
TABLE 1
| Name of the name | Specific 1C Capacity (mAhg) -1 ) | Specific 2C Capacity (mAhg) -1 ) | Specific 5C Capacity (mAhg) -1 ) | Specific 10C Capacity (mAhg) -1 ) |
| Example 1 | 137.3 | 131.9 | 116.6 | 91.3 |
| Example 2 | 130.6 | 123.0 | 110.9 | 87.7 |
| Example 3 | 134.7 | 128.9 | 112.3 | 92.8 |
| Example 4 | 134.9 | 128.6 | 109.2 | 85.0 |
| Example 5 | 131.2 | 121.6 | 105.2 | 83.3 |
| Example 6 | 137.1 | 130.0 | 116.0 | 95.3 |
Comparative example 1:
the difference from example 1 is that in step 1, the molar masses of manganese sulfate and sodium persulfate are 12.84mol and 12.84mol, respectively.
Comparative example 2:
the difference from example 1 is that in step 1, the temperature of the reflux reaction was 80 ℃.
Comparative example 3
The difference from example 1 is that in step 1, the time of the reflux reaction was 24 hours.
Comparative examples 1-3 compared with example 1, the concentration, temperature and time of the solution of the reflux reaction in the precursor synthesis process were respectively changed, and the morphology of the prepared nano manganese oxide precursor is shown in fig. 9-11.
Comparative example 4
Comparative example 4 differs from example 1 in that in step 2, the holding temperature at the time of the heat treatment in the muffle furnace was 850 ℃. Compared with the example 1, the heat treatment temperature in the preparation process of the finished product is changed, and the morphology of the prepared lithium nickel manganese oxide material is shown in figure 12.
The above comparative examples were all assembled in the same manner as in example 1 and were subjected to charge and discharge tests. As shown in table 2, the first-turn discharge capacity and coulombic efficiency of the materials of comparative examples 1 to 4 were significantly reduced compared to the material of example 1.
TABLE 2
| Name of the name | 0.1C first round charging specific capacity (mAh/g) | Specific discharge capacity (mAh/g) of 0.1C first turn | 0.1C first circle coulombic efficiency (%) |
| Example 1 | 148 | 133 | 89.9 |
| Comparative example 1 | 154 | 121 | 78.6 |
| Comparative example 2 | 159 | 116 | 72.8 |
| Comparative example 3 | 166 | 112 | 67.2 |
| Comparative example 4 | 163 | 123 | 73.3 |
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that variations and modifications can be made without departing from the scope of the invention.
Claims (6)
1. The preparation method of the nano rod-shaped lithium nickel manganese oxide positive electrode material is characterized by comprising the following steps of:
s1, according to a mole ratio of 1:1, dissolving a manganese source and sodium persulfate in deionized water, wherein the concentration of manganese ions is 0.1-0.4mol/L, injecting the mixed solution into a reaction kettle for reflux reaction, wherein the reaction temperature is 100-120 ℃, the heat preservation time is 12-15 hours, the mechanical stirring speed is 100-200 rmp, and filtering, washing and drying steps are performed after the reaction is finished to recover a precipitate product; sintering the precipitate for 4-6h at 500-550 ℃ to obtain a nanometer manganese oxide precursor manganese sesquioxide;
s2, mixing the nano manganese oxide precursor with a nickel source and a lithium source according to a molar ratio Mn of Ni:Li=1.5-1.6: 0.5: and (3) after uniformly mixing 1-1.2, sintering at 650-750 ℃ for 18-24 hours in an air atmosphere to obtain the nano rod-shaped lithium nickel manganese oxide anode material which is of a spinel structure and is in a rod shape, wherein the rod length is 500-1 mu m, the diameter is 60-100nm, the surface of the nano rod is rough, and the appearance and the size are uniform.
2. The method for preparing a nano rod-shaped lithium nickel manganese oxide positive electrode material according to claim 1, wherein the manganese source in S1 is one or more of manganese sulfate, manganese acetate and manganese carbonate.
3. The method for preparing a nano rod-shaped lithium nickel manganese oxide positive electrode material according to claim 1, wherein the heating rate of the sintering temperature in the step S1 is 2.5 ℃/min-3.5 ℃/min.
4. The method for preparing a nano rod-shaped lithium nickel manganese oxide positive electrode material according to claim 1, wherein the lithium source S2 is one or more of lithium carbonate, lithium hydroxide and lithium acetate.
5. The method for preparing a nano rod-shaped lithium nickel manganese oxide positive electrode material according to claim 1, wherein the nickel source in S2 is one or more of nickel acetate, nickel nitrate and nickel hydroxide.
6. A lithium ion soft-packed battery is characterized in that the nano rod-shaped lithium nickel manganese oxide positive electrode material prepared by the preparation method of the nano rod-shaped lithium nickel manganese oxide positive electrode material according to any one of claims 1-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410034490.0A CN117543008B (en) | 2024-01-10 | 2024-01-10 | Nano rod-shaped lithium nickel manganese oxide positive electrode material, preparation method and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410034490.0A CN117543008B (en) | 2024-01-10 | 2024-01-10 | Nano rod-shaped lithium nickel manganese oxide positive electrode material, preparation method and battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117543008A CN117543008A (en) | 2024-02-09 |
| CN117543008B true CN117543008B (en) | 2024-03-26 |
Family
ID=89794277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410034490.0A Active CN117543008B (en) | 2024-01-10 | 2024-01-10 | Nano rod-shaped lithium nickel manganese oxide positive electrode material, preparation method and battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117543008B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100107788A (en) * | 2009-03-26 | 2010-10-06 | 한국과학기술원 | Method for preparing lithium manganese oxide and lithium manganese metal oxide with spinel and nanostructure |
| CN102502853A (en) * | 2011-12-18 | 2012-06-20 | 中国科学院电工研究所 | Method for preparing nanometer manganese dioxide by microwave reflux method |
| CN102583561A (en) * | 2012-01-12 | 2012-07-18 | 大连民族学院 | Alpha-phase manganese dioxide nano-rod, and preparation method and application thereof |
| CN102730760A (en) * | 2011-04-07 | 2012-10-17 | 中国科学院城市环境研究所 | Preparation method of 1*1-type manganese oxide octahedral molecular sieves |
| CN103762354A (en) * | 2014-01-22 | 2014-04-30 | 中南大学 | LiNi0.5Mn1.5O4 material, preparation method thereof as well as lithium ion battery |
| CN104409717A (en) * | 2014-11-06 | 2015-03-11 | 奇瑞汽车股份有限公司 | Nano rod-shaped nickel-lithium manganate cathode material and preparation method thereof |
| CN106410185A (en) * | 2016-11-11 | 2017-02-15 | 北京理工大学 | Preparation method for lithium ion battery manganese-based cathode materials of egg yolk-egg shell structure |
| CN107256964A (en) * | 2017-06-14 | 2017-10-17 | 哈尔滨工业大学（威海） | A kind of preparation method of the bar-shaped nickel ion doped of high-voltage lithium-battery cathode material |
| CN108649217A (en) * | 2018-05-09 | 2018-10-12 | 哈尔滨工业大学（威海） | A kind of preparation method of high-voltage lithium-battery cathode material bat mixing nickel ion doped |
| CN109935827A (en) * | 2019-03-25 | 2019-06-25 | 合肥学院 | A kind of preparation method of nano bar-shape nickel ion doped and its application in cell positive material |
| CN114105207A (en) * | 2021-12-01 | 2022-03-01 | 西安交通大学 | High-voltage two-dimensional lithium nickel manganese oxide positive electrode material prepared from porous nano flaky manganese trioxide intermediate and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101983044B1 (en) * | 2017-11-08 | 2019-05-29 | 한국기초과학지원연구원 | Nanorod-shaped cathode active material for a lithium secondary battery, manufacturing method thereof, and lithium secondary battery comprising the same |
-
2024
- 2024-01-10 CN CN202410034490.0A patent/CN117543008B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100107788A (en) * | 2009-03-26 | 2010-10-06 | 한국과학기술원 | Method for preparing lithium manganese oxide and lithium manganese metal oxide with spinel and nanostructure |
| CN102730760A (en) * | 2011-04-07 | 2012-10-17 | 中国科学院城市环境研究所 | Preparation method of 1*1-type manganese oxide octahedral molecular sieves |
| CN102502853A (en) * | 2011-12-18 | 2012-06-20 | 中国科学院电工研究所 | Method for preparing nanometer manganese dioxide by microwave reflux method |
| CN102583561A (en) * | 2012-01-12 | 2012-07-18 | 大连民族学院 | Alpha-phase manganese dioxide nano-rod, and preparation method and application thereof |
| CN103762354A (en) * | 2014-01-22 | 2014-04-30 | 中南大学 | LiNi0.5Mn1.5O4 material, preparation method thereof as well as lithium ion battery |
| CN104409717A (en) * | 2014-11-06 | 2015-03-11 | 奇瑞汽车股份有限公司 | Nano rod-shaped nickel-lithium manganate cathode material and preparation method thereof |
| CN106410185A (en) * | 2016-11-11 | 2017-02-15 | 北京理工大学 | Preparation method for lithium ion battery manganese-based cathode materials of egg yolk-egg shell structure |
| CN107256964A (en) * | 2017-06-14 | 2017-10-17 | 哈尔滨工业大学（威海） | A kind of preparation method of the bar-shaped nickel ion doped of high-voltage lithium-battery cathode material |
| CN108649217A (en) * | 2018-05-09 | 2018-10-12 | 哈尔滨工业大学（威海） | A kind of preparation method of high-voltage lithium-battery cathode material bat mixing nickel ion doped |
| CN109935827A (en) * | 2019-03-25 | 2019-06-25 | 合肥学院 | A kind of preparation method of nano bar-shape nickel ion doped and its application in cell positive material |
| CN114105207A (en) * | 2021-12-01 | 2022-03-01 | 西安交通大学 | High-voltage two-dimensional lithium nickel manganese oxide positive electrode material prepared from porous nano flaky manganese trioxide intermediate and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117543008A (en) | 2024-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tang et al. | Synthesis and electrochemical performance of lithium-rich cathode material Li [Li0. 2Ni0. 15Mn0. 55Co0. 1-xAlx] O2 | |
| CN102738458B (en) | Surface modification method of lithium-rich cathode material | |
| CN105990577B (en) | A kind of anode material for lithium-ion batteries LiNi0.6-xCo0.2Mn0.2AlxO2-yFyAnd preparation method thereof | |
| CN110931797A (en) | High-nickel positive electrode material with composite coating layer and preparation method thereof | |
| CN107834050A (en) | A kind of lithium-enriched cathodic material of lithium ion battery and its improved method | |
| CN105271424B (en) | Preparation method of needle-like spinel lithium manganese oxide positive electrode material | |
| CN111463428A (en) | Sodium ion doped ternary cathode material and preparation method thereof | |
| CN108091854A (en) | A kind of high-voltage spinel type anode material for lithium-ion batteries of Anion-cation multiple dope and preparation method thereof | |
| CN115995531A (en) | Positive electrode active material, positive electrode plate, lithium ion battery and application of positive electrode active material and positive electrode plate | |
| CN112397766A (en) | High-voltage lithium ion battery and preparation method thereof | |
| CN111463427A (en) | Chloride ion doped modified lithium-rich layered cathode material and preparation method thereof | |
| CN103943841A (en) | Anion doped modified lithium ion battery (4:4:2) type ternary cathode material and preparing method thereof | |
| CN109755530B (en) | Surface coating method for titanium barium bimetallic oxide of high-pressure lithium cobalt oxide positive electrode material | |
| CN108400320A (en) | A method of in spinel nickel manganate cathode material for lithium surface sulfide | |
| CN110931770A (en) | Cr-doped modified high-voltage spinel cathode material and preparation method thereof | |
| CN114400315A (en) | Preparation method of layered quaternary positive electrode material of lithium ion battery | |
| CN108039452A (en) | A kind of lithium-rich anode material of nitride cladding and preparation method thereof | |
| CN114613963B (en) | Negative electrode material, preparation method thereof, negative electrode sheet and secondary battery | |
| CN116062797A (en) | Positive electrode material and battery containing same | |
| CN117543008B (en) | Nano rod-shaped lithium nickel manganese oxide positive electrode material, preparation method and battery | |
| CN101764216A (en) | Preparation method for anode material (LiFePO4 powder) of doped lithium ion battery | |
| CN115275088A (en) | Lithium indium aluminum phosphate coated high nickel cobalt lithium tungstate cathode material and preparation method thereof | |
| CN114014330A (en) | Energy storage electrode material K3Nb3Si2O13Preparation method and application of | |
| CN113161534A (en) | Co-doped modified lithium ion battery ternary cathode material and preparation method thereof | |
| CN108011096B (en) | Porous cubic lithium battery cathode material lithium nickel manganese oxide and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |