CN107146877B - Preparation method of fluoxaphosphate lithium ion battery material, positive plate and lithium ion battery - Google Patents
Preparation method of fluoxaphosphate lithium ion battery material, positive plate and lithium ion battery Download PDFInfo
- Publication number
- CN107146877B CN107146877B CN201710304314.4A CN201710304314A CN107146877B CN 107146877 B CN107146877 B CN 107146877B CN 201710304314 A CN201710304314 A CN 201710304314A CN 107146877 B CN107146877 B CN 107146877B
- Authority
- CN
- China
- Prior art keywords
- powder
- life
- ion battery
- lithium ion
- preparation
- 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.)
- Expired - Fee Related
Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 74
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000012002 vanadium phosphate Substances 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011888 foil Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000005955 Ferric phosphate Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229940032958 ferric phosphate Drugs 0.000 claims description 6
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- -1 fluoride oxygen phosphate lithium Chemical compound 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 229920000131 polyvinylidene Polymers 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 229910000398 iron phosphate Inorganic materials 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 description 10
- 239000011812 mixed powder Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 229910010710 LiFePO Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 229910017677 NH4H2 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- FGSXRUYPQWMIRU-UHFFFAOYSA-L lithium fluoro-dioxido-oxo-lambda5-phosphane iron(2+) Chemical compound P(=O)([O-])([O-])F.[Fe+2].[Li+] FGSXRUYPQWMIRU-UHFFFAOYSA-L 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- UMOAGNWVKLAAPT-UHFFFAOYSA-M O.P(=O)(O)(O)[O-].[Li+].[F] Chemical compound O.P(=O)(O)(O)[O-].[Li+].[F] UMOAGNWVKLAAPT-UHFFFAOYSA-M 0.000 description 1
- QRVIVVYHHBRVQU-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O Chemical compound [Li+].[V+5].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O QRVIVVYHHBRVQU-UHFFFAOYSA-H 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of electrochemical energy storage new materials and preparation thereof. The invention provides a preparation method of a fluoxaphosphate lithium ion battery material, a positive plate and a lithium ion battery. The method comprises the following steps: 1) LiFe1‑xVxPO4F1‑δOδ(x ═ 0, 0.1, 0.3, 0.5, 0.7, and 1, δ ≦ 0.4) preparation of powder: according to LiFe1‑xVxPO4F1‑δOδWeighing iron phosphate, vanadium phosphate and lithium source powder according to a metering ratio, grinding, and calcining in inert gas to obtain LiFe1‑xVxPO4F1‑δOδA pure phase powder. LiFe1‑ xVxPO4F1‑δOδPreparing a positive plate: mixing LiFe1‑ xVxPO4F1‑δOδBall milling the pure phase powder and the nano conductive carbon to obtain LiFe1‑xVxPO4F1‑δOδCoating the powder with C, mixing LiFe1‑ xVxPO4F1‑δOδMixing the/C powder and the adhesive according to the mass ratio, dissolving in an organic solvent, coating on an aluminum foil after stirring, and drying to obtain the LiFe1‑xVxPO4F1‑δOδAnd (4) a positive plate. The battery material prepared by the invention has good cycle performance at 0.1C rate.
Description
Technical Field
The invention relates to a fluoroxyphosphate (LiFe)1-xVxPO4F1-δOδ) A preparation method of a lithium ion battery material, a positive plate and a lithium ion battery belong to the technical field of novel electrochemical energy storage materials and preparation thereof.
Background
3.45V lithium iron phosphate (LiFePO) having an olivine structure4) Compared with a lithium ion battery, the lithium iron fluorophosphate (LiFePO) with the Tavorite structure4F) The ionic conductivity of the metal oxide is improved by more than two orders of magnitude, but unfortunately, the working voltage is lower and is only 2.8V, and other high-reduction oxidation couple such as V in a non-fluorine system is used for reference to solve the problem3+/V4+(4.2V) etc. in place of Fe2+/V3+An electric pairing method (B.Yang, et al., J.Phys.chem.Solids,87:228,2015; P.F.Xiao, et al., Solid State Ionics,242:10,2013; J.Barker, et al., electrochem.Solid-State Lett.,8: A285,2005; J.Barker, et al., Eur.Phys.J.Appl.Phys.,35:47749,2004) to improve the technical idea of the fluorine-containing system voltage platform.
Lithium iron fluorophosphate (LiFePO)4F) Lithium vanadium fluorophosphate (LiVPO)4F) Lithium vanadyl phosphate (LiVPO)4O) and solid solutions thereof, most of which relate to the synthesis of a single material, without the presence of a fluorooxyphosphate(LiFe1- xVxPO4F1-δOδ) And (5) related reports.
Disclosure of Invention
Aiming at the defects of the existing battery material, the invention aims to provide a preparation method of a fluoxaphosphate lithium ion battery material, a positive plate and a lithium ion battery.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
fluorooxyphosphate lithium ion battery material LiFe1-xVxPO4F1-δOδThe preparation method of (1), wherein x is 0-1 and δ is not more than 0.4; the method comprises the following steps:
1) according to VPO4Weighing the following components in a metering ratio: grinding and mixing vanadium source and phosphorus source raw materials, calcining for 3-8 hours in inert gas at 200-400 ℃, and cooling to room temperature to obtain powder;
2) grinding and mixing the powder obtained in the step 1) for 0.5-2 hours, calcining the mixture in inert gas at 700-900 ℃ for 4-10 hours, and cooling the mixture to room temperature to obtain VPO4A powder as a main phase;
3)LiFe1-xVxPO4F1-δOδpreparation of powder: according to LiFe1-xVxPO4F1-δOδWeighing ferric phosphate, lithium fluoride powder and the vanadium phosphate prepared in the step 2) according to a metering ratio, and grinding to obtain Li-Fe-V-P-O-F precursor powder, wherein the molar weight of the lithium fluoride powder is 1-1.05 times of the total molar weight of the ferric phosphate and the vanadium phosphate powder;
4) calcining Li-Fe-V-P-O-F precursor powder in inert gas at the temperature of 575-675 ℃ for 1.5-6 hours, and grinding to obtain LiFe1-xVxPO4F1-δOδA pure phase powder.
In the scheme, in the step 1): the vanadium source is one of vanadium trioxide or vanadium pentoxide.
In the scheme, in the step 1): the phosphorus source is one of diammonium hydrogen phosphate or phosphorous acid.
In the above scheme, x is 0.1, 0.3, 0.5, 0.7 or 1.
In the above scheme, the inert gas is argon or nitrogen.
A preparation method of a fluorine oxygen phosphate lithium ion battery positive plate comprises the following steps:
1) mixing the LiFe1-xVxPO4F1-δOδMixing the pure-phase powder and the nano conductive carbon according to the mass ratio of 3: 1-8: 1, and performing ball milling to obtain LiFe1-xVxPO4F1-δOδC carbon-coated powder;
2) mixing LiFe1-xVxPO4F1-δOδMixing the/C powder and polyvinylidene fluoride according to a mass ratio of 9: 1-9.5: 0.5, dissolving in N-methyl pyrrolidone, stirring until the viscosity is 3000-6000 mPa.s, coating on an aluminum foil, and drying in vacuum to obtain LiFe1- xVxPO4F1-δOδAnd (4) a positive plate.
In the scheme, in the step 1): the nano conductive carbon is a carbon particle, a carbon nanotube or a graphene carbon source with a size of less than 100nm in at least one direction.
In the scheme, in the step 1): the ball milling time is 4-8 hours.
In the scheme, in the step 2): LiFe1-xVxPO4F1-δOδThe mass ratio of the/C powder to the N-methyl pyrrolidone is 1: 7-1: 9.
A lithium ion battery comprising a positive electrode sheet as described above.
The invention also provides an assembly of the oxyfluoride phosphate lithium ion battery, which comprises the following steps:
1) mixing LiFe1-xVxPO4F1-δOδAssembling the positive plate, the lithium negative plate, the diaphragm, the electrolyte and the battery case fitting in a glove box with oxygen content and water content lower than 1 ppm;
2) and standing for 10-16 hours after the lithium ion battery is assembled, and carrying out related electrochemical performance tests.
The solute of the electrolyte is one of lithium hexafluorophosphate and lithium dioxalate borate; the solvent of the electrolyte is one or a mixture of several of ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate according to any proportion; the concentration of the electrolyte is 1-1.2 mol/L. The diaphragm is one of a polypropylene diaphragm and a glass fiber diaphragm.
LiFe obtained by the invention1-xVxPO4F1-δOδ(x is 0, 0.1, 0.3, 0.5, 0.7 and 1, delta is not more than 0.4) the first discharge capacity of the lithium ion battery is 150.3 mA.h.g at 20 ℃ (0.1C multiplying power)-1(x=0)、148.4mA·h·g-1(x=0.1)、152.3mA·h·g-1(x=0.3)、191.9mA·h·g-1(x=0.5)、192.6mA·h·g-1(x ═ 0.7) and 191.1mA · h · g-1(x ═ 1), and the discharge capacities were 148.2mA · h · g, respectively, after 30 cycles-1、142.5mA·h·g-1、105mA·h·g-1、10mA·h·g-1、30mA·h·g-1And 1.9 mA. h. g-1The capacity retention rates were 98.8%, 95.20%, 68.94%, 6.03%, 17.78%, and 0.99%, respectively.
The invention has the beneficial effects that:
1. the high capacity of the battery material can be effectively ensured by adopting a nano carbon coating method;
2. synthesize pure phase LiFe1-xVxPO4F1-δOδTraces of (A) are only found possible under very harsh detection conditions<2 wt.%) heterophasic phase;
3. the oxyfluoride phosphate lithium ion battery has very high discharge capacity and capacity retention rate (x is more than or equal to 0 and less than or equal to 0.3, and the stability is good) under the multiplying power of 0.1C.
The invention can be popularized to other fluorophosphate lithium ion battery materials and preparation methods thereof, such as XaMb(PO4)cFdO1-d(X ═ Li, Na or mixtures thereof; M ═ Fe, V, Mn, Ni, Co, Cu, Ti, Al, Cr, Mo, Nb or mixtures thereof; 0<a≤5,0<b≤3,0<c is less than or equal to 3, d is 0.1-1) and the like, and a preparation method thereof.
Drawings
FIG. 1 is a LiFe prepared in example one1-xVxPO4F1-δOδX-ray diffraction (XRD) pattern of the powder.
Fig. 2 is a charge-discharge cycle curve of the fluorophosphate lithium ion battery prepared in the first embodiment under 20 ℃ (0.1C rate).
Fig. 3 is a charge-discharge cycle curve of the lithium ion battery of the fluorophosphates prepared in example four under 20 ℃ (0.1C rate).
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
The first embodiment is as follows:
a preparation method of a fluoxaphosphate lithium ion battery material comprises the following steps:
s1.1 according to VPO4Weighing V in metering ratio2O5And H3PO3Grinding and mixing the raw materials, sieving the raw materials by using a 120-mesh sieve, and batching the raw materials to obtain V-P-O mixed powder. And presintering the mixed powder in argon at 300 ℃ for 6 hours, and cooling to room temperature to obtain powder. Grinding the powder for 0.5 hour, calcining at 870 deg.C for 8 hours in argon gas, cooling to room temperature to obtain VPO4Powder of the main phase.
S1.2 according to LiFe1-xVxPO4F1-δOδWeighing commercially available ferric phosphate, vanadium phosphate prepared from S1.1 and lithium fluoride powder (the molar amount of the lithium fluoride powder is 1.05 times of the total molar amount of the ferric phosphate and the vanadium phosphate powder) according to the metering ratio (x is 0, 0.1, 0.3, 0.5, 0.7 and 1, and delta is less than or equal to 0.4), and grinding to obtain Li-Fe-V-P-O-F precursor powder;
s1.3 calcining Li-Fe-V-P-O-F precursor powder in argon at 625 ℃ for 4.5 hours, and grinding for 1 hour to obtain LiFe1-xVxPO4F1-δOδA pure phase powder.
S1.4 reaction of LiFe1-xVxPO4F1-δOδMixing the pure phase powder and the nano conductive carbon according to the mass ratio of 7:2, and performing ball milling for 8 hours to obtain LiFe1-xVxPO4F1-δOδC carbon-coated powder.
S1.5 reacting LiFe1-xVxPO4F1-δOδMixing the/C powder with a polyvinylidene fluoride adhesive in a mass ratio of 9:1, dissolving in N-methyl pyrrolidone, and obtaining LiFe1-xVxPO4F1-δOδThe mass ratio of the/C powder to the N-methyl pyrrolidone is 1:7, the mixture is coated on an aluminum foil when the mixture is stirred until the viscosity is 3000mPa & s, and the mixture is dried in vacuum to obtain LiFe1-xVxPO4F1-δOδA positive plate;
S1.6LiPF6EC/DMC electrolyte: the concentration of the electrolyte is 1mol/L, and the solute is LiPF6The solvent was EC/DMC (1:1, vol.%).
S1.7 reacting LiFe1-xVxPO4F1-δOδAssembling the positive plate, the lithium negative plate, the polypropylene diaphragm, the electrolyte and the battery shell fitting in a glove box with oxygen content and water content lower than 1ppm, wherein the concentration of the electrolyte is 1mol/L, and the solute is LiPF6The solvent was EC/DMC (1:1, vol.%). After the assembly, the mixture was allowed to stand for 10 hours and subjected to a charge-discharge cycle at 20 ℃ (0.1C magnification).
FIG. 1 is a LiFe prepared in example one1-xVxPO4F1-δOδX-ray diffraction (XRD) pattern of the powder, the results show that: the invention synthesizes a series of LiFe1-xVxPO4F1-δOδPure phase powder of LiFe1-xVxPO4F1-δOδThe pure phase powders are respectively marked LFPF (LiFePO)4F)、LF0.9V0.1PF1-δOδ(LFe0.9V0.1PO4F1-δOδ)、LF0.7V0.3PF1-δOδ(LFe0.7V0.3PO4F1-δOδ)、LF0.5V0.5PF1-δOδ(LFe0.5V0.5PO4F1-δOδ)、LF0.3V0.7PF1-δOδ(LFe0.3V0.7PO4F1-δOδ)、LVPF1-δOδ(LVPO4F1-δOδ)。
Fig. 2 is a charge-discharge cycle curve of the lithium-ion oxyfluoride phosphate battery prepared in the first example at 20 ℃ (0.1C rate). It can be seen that the discharge plateaus of the batteries are about 2.8V and 4.2V, and the first discharge capacities are 150.3 mA.h.g-1(x=0)、148.4mA·h·g-1(x=0.1)、152.3mA·h·g-1(x=0.3)、191.9mA·h·g-1(x=0.5)、192.6mA·h·g-1(x ═ 0.7) and 191.1mA · h · g-1(x ═ 1), the capacity gradually increased with increasing vanadium content. When the discharge capacity is circulated for 30 times, the discharge capacity is respectively 148.2 mA.h.g-1、142.5mA·h·g-1、105mA·h·g-1、10mA·h·g-1、30mA·h·g-1And 1.9 mA. h. g-1The capacity retention rates are respectively 98.8%, 95.20%, 68.94%, 6.03%, 17.78% and 0.99%, LiFe1-xVxPO4F1-δOδ(x is more than or equal to 0 and less than or equal to 0.3), good cycle stability and LiFe1-xVxPO4F1-δOδAmong the series batteries, LFe0.9V0.1PO4F1-δOδThe comprehensive performance is best, the first discharge capacity and the cycle performance are excellent, and the LiFePO has two discharge voltage platforms of 2.8V and 4.2V4The performance of the F battery is excellent, but the battery has a discharge voltage platform of only 2.8V and has lower voltage.
Example two:
the second example was the same as the first example except that the V-P-O mixed powder was changed in the raw material, calcination temperature and time.
S1.1 according to VPO4Weighing V in metering ratio2O3And NH4H2PO4Grinding and mixing the raw materials, sieving the raw materials by using a 120-mesh sieve, and batching the raw materials to obtain V-P-O mixed powder. Presintering the mixed powder in argon gas at 200 ℃ for 8 hours to obtain powderGrinding for 2 hours, calcining in argon at 700 ℃ for 10 hours to obtain VPO4Powder as the main phase, LiFe was obtained according to the procedure of example one1-xVxPO4F1-δOδThe discharge capacities of the batteries were 126.5mA · h · g, respectively, when the batteries were cycled up to 30 times-1(x=0)、81.9mA·h·g-1(x=0.1)、0.6mA·h·g-1(x=0.3)、6.3mA·h·g-1(x=0.5)、22.7mA·h·g-1(x ═ 0.7) and 5.4mA · h · g-1(x ═ 1), the capacity retention rate was 94.21%, 71.35%, 2.13%, 3.12%, 9.28%, and 2.35%.
Example three:
the calcination temperature and time of the V-P-O mixed powder in example III were the same as those in example I except that they were changed.
S1.1 preparing V-P-O mixed powder according to example II, presintering the mixed powder in argon gas at 400 ℃ for 3 hours, grinding the obtained powder for 2 hours, and calcining the powder in argon gas at 900 ℃ for 4 hours to obtain VPO4Powder as the main phase, LiFe was obtained according to the procedure of example one1-xVxPO4F1-δOδThe discharge capacities of the batteries were 125.8mA · h · g, respectively, when the batteries were cycled for 30 times-1(x=0)、75.6mA·h·g-1(x=0.1)、1.5mA·h·g-1(x=0.3)、7.2mA·h·g-1(x=0.5)、23.5mA·h·g-1(x ═ 0.7) and 6.2mA · h · g-1(x ═ 1), the capacity retention was 95.71%, 74.52%, 3.26%, 4.27%, 9.12%, and 2.17%.
Comparative example one:
the comparative example was identical to example one, except that the preparation method of the V-P-O mixed powder (carbothermic method) was different.
S1.1 according to VPO4Weighing V in metering ratio2O5、NH4H2PO4And carbon powder (25% excess), milling, mixing, and calcining at 750 ℃ for 4 hours in argon to obtain VPO4The target product was obtained according to the procedure of example one, and XRD results of the target product showed that LiFe was not synthesized1-xVxPO4F1-δOδPowder and more impurity phases, which are fully explained in the preparation of LiFe1- xVxPO4F1-δOδIn the process of preparing the powder, VPO is prepared by adopting a carbothermic method4The powder, in which carbon powder is mixed, may reduce ferric ions to ferrous ions in minute amounts, further resulting in experimental failure.
Example four:
example four was the same as example one, except that the calcination temperature and time of the Li-Fe-V-P-O-F precursor powder were different.
S1.1 preparing Li-Fe-V-P-O-F precursor powder according to the first embodiment, calcining the Li-Fe-V-P-O-F precursor powder in argon at 625 ℃ for 1.5 hours, and grinding to obtain LiFe1-xVxPO4F1-δOδA pure phase powder.
FIG. 3 is a charge-discharge cycle curve of the lithium ion battery of oxyfluoride phosphate obtained in example four at 20 deg.C (0.1C rate), and it can be seen that the discharge capacities were 125.3mA h g respectively at 30 cycles-1(x=0)、84.4mA·h·g-1(x=0.1)、0.1mA·h·g-1(x=0.3)、32.7mA·h·g-1(x=0.5)、31.5mA·h·g-1(x ═ 0.7) and 64.9mA · h · g-1(x ═ 1), the capacity retention ratio was 92.19%, 80.84%, 0.11%, 21.21%, 25.09%, and 38.44%.
Example five:
example five is the same as example one, except that the calcination temperature and time of the Li-Fe-V-P-O-F precursor powder were different.
S1.1 calcining Li-Fe-V-P-O-F precursor powder in argon at 575 ℃ for 6 hours, and grinding to obtain LiFe1- xVxPO4F1-δOδA pure phase powder. Thus obtaining LiFe1-xVxPO4F1-δOδThe discharge capacities of the batteries were 116.5mA · h · g, respectively, when the batteries were cycled up to 30 times-1(x=0)、82.3mA·h·g-1(x=0.1)、0.5mA·h·g-1(x=0.3)、4.2mA·h·g-1(x=0.5)、21.2mA·h·g-1(x ═ 0.7) and 4.5mA · h · g-1(x ═ 1), the capacity retention ratio was 93.12%, 70.35%, 0.13%, 2.52%, 10.98%, and 2.47%.
Example six:
example six is the same as example one, except that the calcination temperature and time of the Li-Fe-V-P-O-F precursor powder were varied.
S1.1 calcining Li-Fe-V-P-O-F precursor powder for 1.5 hours in argon at 675 ℃, and grinding to obtain LiFe1- xVxPO4F1-δOδA pure phase powder. Thus obtaining LiFe1-xVxPO4F1-δOδThe discharge capacities of the batteries were 113.2mA · h · g, respectively, when the batteries were cycled up to 30 times-1(x=0)、81.9mA·h·g-1(x=0.1)、0.4mA·h·g-1(x=0.3)、3.6mA·h·g-1(x=0.5)、22.3mA·h·g-1(x ═ 0.7) and 4.3mA · h · g-1(x ═ 1), the capacity retention ratio was 94.27%, 71.27%, 0.15%, 2.56%, 10.87%, and 2.61%.
Example seven:
example seven is the same as example one, except that the proportions of the conductive agent, the binder and the solvent are different.
S1.1 Life from example one1-xVxPO4F1-δOδMixing the pure phase powder and the nano conductive carbon according to the mass ratio of 8:1, and performing ball milling for 4 hours to obtain LiFe1-xVxPO4F1-δOδC carbon-coated powder.
S1.2 reacting LiFe1-xVxPO4F1-δOδMixing the/C powder with polyvinylidene fluoride adhesive in a mass ratio of 9.5:0.5, dissolving in N-methyl pyrrolidone, and obtaining LiFe1-xVxPO4F1-δOδThe mass ratio of the/C powder to the N-methyl pyrrolidone is 1:9, the mixture is stirred until the viscosity is 6000 mPa.s, the mixture is coated on an aluminum foil, and the mixture is dried in vacuum to obtain LiFe1-xVxPO4F1-δOδA positive plate; LiFe thus obtained1-xVxPO4F1-δOδWhen the battery is cycled for 30 times, the discharge capacity is respectively 112.7 mA.h.g-1(x=0)、76.8mA·h·g-1(x=0.1)、0.7mA·h·g-1(x=0.3)、2.3mA·h·g-1(x=0.5)、21.2mA·h·g-1(x ═ 0.7) and 4.5mA · h · g-1(x ═ 1), the capacity retention ratio was 97.62%, 81.32%, 1.45%, 3.27%, 11.23%, and 4.52%.
Comparative example two:
the comparative example was the same as example one except that the kind of the conductive agent was different.
S1.1 Life from example one1-xVxPO4F1-δOδMixing the pure phase powder and acetylene black according to the mass ratio of 7:2, and performing ball milling to obtain LiFe1-xVxPO4F1-δOδC carbon-coated powder. LiFe thus obtained1-xVxPO4F1-δOδWhen the battery is cycled for 30 times, the discharge capacity is 65.89 mA.h.g-1(x=0)、56.72mA·h·g-1(x=0.1)、0.1mA·h·g-1(x=0.3)、1.1mA·h·g-1(x=0.5)、11.7mA·h·g-1(x ═ 0.7) and 2.5mA · h · g-1(x ═ 1), the capacity retention was 97.62%, 81.32%, 1.45%, 3.27%, 11.23%, and 4.52%, and the electrochemical performance tested was very poor.
Claims (10)
1. A preparation method of a fluoxaphosphate lithium ion battery material, wherein x is more than 0 and less than 1, and delta is less than or equal to 0.4; the method is characterized by comprising the following steps:
1) according to VPO4Weighing the following components in a metering ratio: grinding and mixing vanadium source and phosphorus source raw materials, calcining for 3-8 hours in inert gas at 200-400 ℃, and cooling to room temperature to obtain powder;
2) grinding and mixing the powder obtained in the step 1) for 0.5-2 hours, calcining the mixture in inert gas at 700-900 ℃ for 4-10 hours, and cooling the mixture to room temperature to obtain VPO4A powder as a main phase;
3)LiFe1-xVxPO4F1-δOδpreparation of powder: according to LiFe1-xVxPO4F1-δOδWeighing ferric phosphate, lithium fluoride powder and the vanadium phosphate prepared in the step 2) according to a metering ratio, and grinding to obtain Li-Fe-V-P-O-F precursor powder, wherein the molar weight of the lithium fluoride powder is 1-1.05 times of the total molar weight of the ferric phosphate and the vanadium phosphate powder;
4) calcining Li-Fe-V-P-O-F precursor powder in inert gas at the temperature of 575-675 ℃ for 1.5-6 hours, and grinding to obtain LiFe1-xVxPO4F1-δOδA pure phase powder.
2. The method of claim 1, wherein in step 1): the vanadium source is one of vanadium trioxide or vanadium pentoxide.
3. The method of claim 1, wherein in step 1): the phosphorus source is one of diammonium hydrogen phosphate or phosphorous acid.
4. The method of claim 1, wherein x is 0.1, 0.3, 0.5, or 0.7.
5. The method of claim 1, wherein the inert gas is argon or nitrogen.
6. A preparation method of a fluoride oxygen phosphate lithium ion battery positive plate is characterized by comprising the following steps:
1) reacting the LiFe of any one of claims 1 to 51-xVxPO4F1-δOδMixing the pure-phase powder and the nano conductive carbon according to the mass ratio of 3: 1-8: 1, and performing ball milling to obtain LiFe1-xVxPO4F1-δOδC carbon-coated powder;
2) mixing LiFe1-xVxPO4F1-δOδPowder of/C and polyvinylidene fluorideMixing ethylene according to the mass ratio of 9: 1-9.5: 0.5, dissolving the mixture in N-methyl pyrrolidone, stirring the mixture until the viscosity is 3000-6000 mPa.s, coating the mixture on an aluminum foil, and drying the aluminum foil in vacuum to obtain LiFe1- xVxPO4F1-δOδAnd (4) a positive plate.
7. The method of claim 6, wherein in step 1): the nano conductive carbon is a carbon particle, a carbon nanotube or a graphene carbon source with a size of less than 100nm in at least one direction.
8. The method of claim 6, wherein in step 1): the ball milling time is 4-8 hours.
9. The method of claim 6, wherein in step 2): LiFe1-xVxPO4F1-δOδThe mass ratio of the/C powder to the N-methyl pyrrolidone is 1: 7-1: 9.
10. A lithium ion battery, characterized in that it comprises a positive electrode sheet as defined in any one of claims 6 to 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710304314.4A CN107146877B (en) | 2017-05-03 | 2017-05-03 | Preparation method of fluoxaphosphate lithium ion battery material, positive plate and lithium ion battery |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710304314.4A CN107146877B (en) | 2017-05-03 | 2017-05-03 | Preparation method of fluoxaphosphate lithium ion battery material, positive plate and lithium ion battery |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107146877A CN107146877A (en) | 2017-09-08 |
CN107146877B true CN107146877B (en) | 2021-02-19 |
Family
ID=59774299
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710304314.4A Expired - Fee Related CN107146877B (en) | 2017-05-03 | 2017-05-03 | Preparation method of fluoxaphosphate lithium ion battery material, positive plate and lithium ion battery |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107146877B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11955624B2 (en) * | 2020-10-29 | 2024-04-09 | Saft America | Blended cathode materials for secondary batteries |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102447096A (en) * | 2010-10-08 | 2012-05-09 | 中国科学院理化技术研究所 | Lithium ferrovanadium phosphate solid solution for positive material of lithium ion battery and preparation and application thereof |
CN105914344A (en) * | 2016-04-13 | 2016-08-31 | 武汉理工大学 | High temperature-stable lithium iron fluorphosphate type lithium ion battery material and preparation method thereof |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101186289A (en) * | 2006-11-17 | 2008-05-28 | 喻维杰 | Method for producing lithium iron phosphate material by vacuum rotary kiln |
CN101719548A (en) * | 2009-11-05 | 2010-06-02 | 翟东军 | Compound lithium iron phosphate used as positive pole material of lithium ion battery and preparation method thereof |
JP5359823B2 (en) * | 2009-11-30 | 2013-12-04 | 株式会社エクォス・リサーチ | Positive electrode active material and secondary battery using the same |
CN102136575A (en) * | 2010-01-22 | 2011-07-27 | 中盛动力新能源投资有限公司保康青山能源研究所 | Lithium ion battery positive-pole material and preparation method thereof |
CN101789504B (en) * | 2010-03-17 | 2012-03-14 | 中南大学 | Preparation method of nano LiFel-xMxPO4/C lithium phosphate composite positive pole material |
CN103066278B (en) * | 2012-11-06 | 2015-07-29 | 浙江南都电源动力股份有限公司 | LiFePO 4 material of the coated vanadium doping of tin oxide and preparation method thereof |
-
2017
- 2017-05-03 CN CN201710304314.4A patent/CN107146877B/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102447096A (en) * | 2010-10-08 | 2012-05-09 | 中国科学院理化技术研究所 | Lithium ferrovanadium phosphate solid solution for positive material of lithium ion battery and preparation and application thereof |
CN105914344A (en) * | 2016-04-13 | 2016-08-31 | 武汉理工大学 | High temperature-stable lithium iron fluorphosphate type lithium ion battery material and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
Oxidation under Air of Tavorite LiVPO4F: Influence of Vanadyl-Type Defects on Its Electrochemical Properties;Edouard Boivin et.al;《The journal of physical chemistry》;20161024;第26187-26198页 * |
Strong Impact of the Oxygen Content in Na3V2(PO4)2F3−yOy (0≤y≤0.5) on Its Structural and Electrochemical Properties;Thibault Broux et.al;《Chemistry of Materials》;20161006;第7683-7692页 * |
Also Published As
Publication number | Publication date |
---|---|
CN107146877A (en) | 2017-09-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zhao et al. | Effect of particle size and purity on the low temperature electrochemical performance of LiFePO4/C cathode material | |
Croguennec et al. | Recent achievements on inorganic electrode materials for lithium-ion batteries | |
JP4654686B2 (en) | Carbon-coated Li-containing powder and method for producing the same | |
JP6011989B2 (en) | Lithium titanium sulfide, lithium niobium sulfide and lithium titanium niobium sulfide | |
Pang et al. | Enhanced rate-capability and cycling-stability of 5 V SiO2-and polyimide-coated cation ordered LiNi0. 5Mn1. 5O4 lithium-ion battery positive electrodes | |
Kou et al. | Role of cobalt content in improving the low-temperature performance of layered lithium-rich cathode materials for lithium-ion batteries | |
JP2023522808A (en) | Negative electrode active material for battery and manufacturing method thereof, battery negative electrode, battery | |
KR20110132566A (en) | Method for producing positive electrode active material for lithium ion battery, positive electrode active material for lithium ion battery, electrode for lithium ion battery, and lithium ion battery | |
CN102306791B (en) | Method for preparing carbon-cladding non-stoichiometric lithium iron phosphorous oxide material | |
CN107611429B (en) | Sodium-rich vanadium iron phosphate sodium material, preparation method thereof and application thereof in sodium-ion battery | |
He et al. | Effect of Nb doping on the behavior of NCA cathode: Enhanced electrochemical performances from improved lattice stability towards 4.5 V application | |
Lu et al. | New-type NASICON-Na4FeV (PO4) 3 cathode with high retention and durability for sodium ion batteries | |
CN103594708B (en) | One is appraised at the current rate iron-based composite positive pole and preparation method thereof | |
CN103165896A (en) | Method for preparing lithium iron phosphate/carbon composite material by thickener doping modification | |
Zhang et al. | Synthesis and characterization of multi-layer core–shell structural LiFeBO3/C as a novel Li-battery cathode material | |
Wang et al. | Effect of Ni doping on electrochemical performance of Li3V2 (PO4) 3/C cathode material prepared by polyol process | |
CN102931404A (en) | Phosphate potential boron-doped manganese phosphate lithium / carbon composite materials and preparation method thereof | |
Zhang et al. | Novel synthesis of LiMnPO4· Li3V2 (PO4) 3/C composite cathode material | |
Sharma et al. | Polyanionic insertion hosts for aqueous rechargeable batteries | |
CN109980221B (en) | High-voltage lithium ion battery positive electrode material and preparation method and application thereof | |
KR20080006928A (en) | Method of manufacturing lithium iron phosphate | |
CN107230779B (en) | Preparation method of high-temperature stable phase-change type lithium iron fluorosulfate battery material, electrode plate and use method of lithium ion battery | |
CN107146877B (en) | Preparation method of fluoxaphosphate lithium ion battery material, positive plate and lithium ion battery | |
Li et al. | Synthesis and electrochemical performance of 0.6 Li3V2 (PO4) 3· 0.4 Li–V–O composite cathode material for lithium ion batteries | |
KR101233410B1 (en) | Cathode active material for lithium secondary battery, method for preparing same, and lithium battery comprising 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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210219 |
|
CF01 | Termination of patent right due to non-payment of annual fee |