CN115340079A - Superfine lithium vanadium phosphate nano-microcrystal integrated chip and preparation method and application thereof - Google Patents
Superfine lithium vanadium phosphate nano-microcrystal integrated chip and preparation method and application thereof Download PDFInfo
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- CN115340079A CN115340079A CN202210890589.1A CN202210890589A CN115340079A CN 115340079 A CN115340079 A CN 115340079A CN 202210890589 A CN202210890589 A CN 202210890589A CN 115340079 A CN115340079 A CN 115340079A
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- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 title claims abstract description 101
- 239000013081 microcrystal Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000011267 electrode slurry Substances 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- 239000002482 conductive additive Substances 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000006230 acetylene black Substances 0.000 claims description 8
- 239000002707 nanocrystalline material Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 102000020897 Formins Human genes 0.000 claims description 3
- 108091022623 Formins Proteins 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 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
- 238000013019 agitation Methods 0.000 claims 1
- 239000013080 microcrystalline material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000009831 deintercalation Methods 0.000 abstract description 3
- 230000020169 heat generation Effects 0.000 abstract description 3
- 238000009830 intercalation Methods 0.000 abstract description 3
- 230000002687 intercalation Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- -1 compound lithium vanadium phosphate Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000009791 electrochemical migration reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—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
- H01M4/13—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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a superfine lithium vanadium phosphate nano microcrystal integrated chip and a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing graphene oxide, a vanadium source, a lithium source and a phosphorus source into a mixed solution, adding a reducing agent into the mixed solution after ultrasonic stirring, and freeze-drying after reaction to obtain lithium vanadium phosphate precursor powder; sintering the lithium vanadium phosphate precursor powder under a protective atmosphere to obtain a lithium vanadium phosphate nano microcrystalline material; and mixing the lithium vanadium phosphate nano microcrystal material, a conductive additive, a binder and an organic solvent to prepare electrode slurry, coating the electrode slurry on a current collector, and drying to obtain the superfine lithium vanadium phosphate nano microcrystal integrated sheet. The superfine lithium vanadium phosphate nano microcrystal integrated chip provided by the invention can relieve the heat generation effect caused by lithium ion intercalation and deintercalation, further improve the safety performance of the material, and ensure that the safety performance does not become an obstacle in the application of lithium ion batteries any more.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage, in particular to an ultrafine lithium vanadium phosphate nano microcrystal integrated chip and a preparation method and application thereof.
Background
The lithium ion battery is a representative of modern high-performance batteries, and the main components of the lithium ion battery comprise a positive electrode material, a negative electrode material, electrolyte, a diaphragm, a binder and the like; the positive electrode material is one of the most important components of the lithium ion battery, and has important influence on the safety, energy density and electrochemical performance of the battery. The currently used mainstream positive electrode materials comprise lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium manganese oxide and the like, wherein the lithium iron phosphate has the advantages of higher safety and high temperature resistance and has the defects of poor low-temperature performance and low energy density; the lithium nickel cobalt manganese oxide has the advantages of high energy density and high voltage platform, and has the disadvantages of poor safety performance and short service life; the lithium manganate has the advantages of simple preparation and higher safety, and has the disadvantages of poor high-temperature resistance and short service life; because the performance difference of the existing materials is large, the advantages and the disadvantages are obvious, and the imbalance of the performance of the anode material limits the wide application of the lithium ion battery.
In addition, the reaction of the anode material and the electrolyte also generates heat, microscopic changes of the surface of the material are caused, the resistance of lithium ion insertion and extraction is increased, the diffusion rate of lithium ions in an electrode is reduced, and the safety performance of the lithium ion battery is also influenced.
Lithium vanadium phosphate nano-crystallites, as a novel material capable of industrial mass production and application, have been applied in the field of lithium ion batteries, but most of these technical solutions dope or compound lithium vanadium phosphate with other materials, and then apply the doped or compounded materials to batteries so as to improve the cycle life of the batteries, and do not relate to the safety performance of the batteries and solutions thereof.
Disclosure of Invention
In view of the above, the invention provides an ultrafine lithium vanadium phosphate nanocrystalline integrated chip, and a preparation method and an application thereof, so as to solve the problems of high heat generation and poor safety when the existing lithium vanadium phosphate acts on a lithium battery electrode.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of an ultrafine lithium vanadium phosphate nano microcrystal integrated chip comprises the following steps:
s1, preparing graphene oxide, a vanadium source, a lithium source and a phosphorus source into a mixed solution, adding a reducing agent into the mixed solution after ultrasonic stirring, and freeze-drying after reaction to obtain lithium vanadium phosphate precursor powder;
s2, sintering the lithium vanadium phosphate precursor powder under a protective atmosphere to obtain a lithium vanadium phosphate nano microcrystalline material;
and S3, mixing the lithium vanadium phosphate nano microcrystal material, a conductive additive, a binder and an organic solvent to prepare electrode slurry, coating the electrode slurry on a current collector, and drying to obtain the superfine lithium vanadium phosphate nano microcrystal integrated chip.
According to the scheme, in the step S1, the mass ratio of the graphene oxide to the vanadium source to the lithium source to the phosphorus source to the oxalic acid is (0.1-1): (3-5): (1-2): (3-5): (0.5-1.5).
According to the scheme, the vanadium source comprises vanadium pentoxide or ammonium metavanadate, the lithium source comprises one of lithium carbonate, lithium oxalate and lithium nitrate, the phosphorus source comprises phosphoric acid, and the reducing agent comprises oxalic acid or acetic acid.
According to the scheme, the ultrasonic stirring temperature is 10-30 ℃, and the stirring time is 30-60min.
According to the scheme, in the step S2, the sintering temperature is 200-500 ℃, the heat preservation time is 1-5h, and the heating rate is 2-10 ℃ for min-1.
According to the scheme, in the step S3, the mass ratio of the lithium vanadium phosphate nano microcrystal material to the conductive additive to the binder is (5-8) to (1-4).
According to the scheme, the conductive additive is acetylene black, the binder is polyvinylidene fluoride (PVDF), the organic solvent is ethanol or N-methylpyrrolidone, and the current collector comprises an aluminum foil.
On the basis of the scheme, the second purpose of the invention is to provide the superfine lithium vanadium phosphate nano-microcrystal integrated chip prepared by the preparation method.
According to the scheme, the superfine lithium vanadium phosphate nano microcrystal integrated chip comprises a current collector and an electrode layer coated on the surface of the current collector, wherein the thickness of the electrode layer is within the range of 10-300 micrometers.
On the basis of the scheme, the third purpose of the invention is to provide the application of the superfine lithium vanadium phosphate nano microcrystal integrated chip in the field of lithium ion batteries.
Compared with the prior art, the invention has the following advantages:
(1) The superfine lithium vanadium phosphate nano microcrystal integrated chip provided by the invention adopts a vanadium material with good safety, the heat production effect caused by lithium ion intercalation and deintercalation is obviously reduced, and a button cell assembled by serving as an anode and a graphite cathode has good cycle performance and safety performance.
(2) The preparation method provided by the invention is simple to operate, low in cost and suitable for industrial production.
Drawings
In order to more clearly illustrate the technical solutions of the present invention or the prior art, some brief descriptions will be given below to the drawings used in the description of the embodiments or the prior art, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a TEM image of a lithium vanadium phosphate nanocrystalline material according to example 1 of the present invention;
FIG. 2 is an SEM picture of lithium vanadium phosphate nanocrystalline material according to example 1 of the invention;
FIG. 3 is an XPS plot of lithium vanadium phosphate nanocrystalline material according to example 1 of the present invention;
fig. 4 is a specific capacity-voltage-cycle curve diagram of a button full battery assembled by the ultra-fine lithium vanadium phosphate nano-crystallite integrated sheet and a graphite cathode at normal temperature in embodiment 1 of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
It should be noted that in the description of the embodiments herein, the description of the term "some embodiments" means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same implementation or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The term "in.
The embodiment of the invention provides a preparation method of a superfine lithium vanadium phosphate nano microcrystal integrated chip, which comprises the following steps:
s1, preparing a mixed solution of graphene oxide, a vanadium source, a lithium source and a phosphorus source, performing ultrasonic stirring at the temperature of 10-30 ℃ for 30-60min, adding a reducing agent into the mixed solution, and performing freeze drying after reaction to obtain lithium vanadium phosphate precursor powder.
Specifically, graphene oxide is prepared into a solution A, a vanadium source, a lithium source and a phosphorus source are prepared into a solution B, the solution A and the solution B are mixed and stirred uniformly, then a reducing agent is added, and freeze drying is carried out after uniform stirring, so that lithium vanadium phosphate precursor powder is obtained.
Further, the mass fraction of the reducing agent added is 20-60% wt.
Wherein the mass ratio of the graphene oxide to the vanadium source to the lithium source to the phosphorus source to the oxalic acid is (0.1-1): (3-5): (1-2): (3-5): (0.5-1.5) the source of vanadium comprises vanadium pentoxide or ammonium metavanadate, the source of lithium comprises one of lithium carbonate, lithium oxalate and lithium nitrate, the source of phosphorus comprises phosphoric acid and the reducing agent comprises oxalic acid or acetic acid.
And S2, sintering the lithium vanadium phosphate precursor powder under a protective atmosphere to obtain the superfine lithium vanadium phosphate nano microcrystal material.
Specifically, the protective atmosphere comprises nitrogen or argon, the sintering temperature is 200-500 deg.C, the heat preservation time is 1-5h, and the heating rate is 2-10 deg.C for min -1 。
Wherein, the size of the superfine lithium vanadium phosphate nano microcrystal material is in the range of 100nm to 200nm, and the length-diameter ratio is in the range of 100.
And S3, taking the lithium vanadium phosphate nano microcrystal material as an active material, mixing the active material, a conductive additive, a binder and an organic solvent to prepare electrode slurry, coating the electrode slurry on a current collector, and drying to obtain the superfine lithium vanadium phosphate nano microcrystal integrated sheet.
Wherein the mass ratio of the lithium vanadium phosphate nano microcrystal material to the conductive additive to the binder is (5-8) to (1-4), and the solid-liquid ratio of the electrode slurry is in the range of 0.1.
Preferably, the conductive additive is acetylene black, the binder is polyvinylidene fluoride (PVDF), the organic solvent is ethanol or N-methyl pyrrolidone, and the current collector comprises aluminum foil.
The preparation process of the electrode slurry needs stirring, the stirring temperature is 20-60 ℃, and the total stirring time is 1-5h; and coating the electrode slurry on a current collector, and drying at the temperature of 80-110 ℃ for 1-5h.
Among them, the following principles are required to be satisfied in determining an electrode active material: the preparation temperature of the superfine lithium vanadium phosphate nano microcrystal integrated chip is lower than the melting point of the current collector.
Therefore, the superfine lithium vanadium phosphate electrode active material and the organic solvent are uniformly mixed to prepare slurry, and then the slurry is coated on the current collector to prepare the superfine lithium vanadium phosphate nano microcrystal integrated sheet, so that the graphene oxide coats the lithium vanadium phosphate and is loaded on the surface of the current collector together; in the sintering process, the graphene oxide is gradually embedded into the lithium vanadium phosphate crystal to form a pre-embedding structure, the crystal gap of the lithium vanadium phosphate is enlarged, but the crystal structure of the lithium vanadium phosphate is not damaged, the graphene oxide and the lithium vanadium phosphate are kept in a stable co-embedding form, the enlarged crystal gap is larger than the diameter of a lithium ion, the embedding and de-embedding of the ion can be effectively improved, and after the long-term use, the co-embedding of the graphene oxide and the lithium vanadium phosphate is tighter, so that the long-term stability of the material is ensured, and the existing material cannot achieve the purpose. After the ions are pre-embedded, a transmission tunnel of the lithium ions in the material is widened, the heat generation effect caused by the embedding and the releasing of the lithium ions is relieved, and the safety performance of the material is further improved.
The preparation method is simple to operate, low in cost and suitable for industrial production; by using the vanadium active material with excellent safety performance, the ionic migration impedance of the battery in charge-discharge overcharge is obviously reduced, and Li is improved + The ion conductivity of the lithium ion battery is improved finally; by constructing ordered arrangement of crystals, the ionic conductivity is increased, the cycle performance at low temperature is enhanced, and the superfine lithium vanadium phosphate nano microcrystal integrated chip can be used as a powerful substitute of the existing lithium ion anode material.
The invention also provides an ultrafine lithium vanadium phosphate nano microcrystal integrated chip prepared by the preparation method.
The superfine lithium vanadium phosphate nano microcrystal integrated sheet comprises a current collector and an electrode layer coated on the surface of the current collector, wherein the thickness of the electrode layer is within the range of 10-300 mu m.
The invention also provides an application of the superfine lithium vanadium phosphate nano microcrystal integrated chip in the field of lithium ion batteries.
The superfine lithium vanadium phosphate nano microcrystal integrated chip provided by the invention adopts a vanadium material with good safety, the heat production effect caused by lithium ion intercalation and deintercalation is obviously reduced, and a button lithium ion battery assembled by serving as an anode and a graphite cathode has good cycle performance and safety performance.
On the basis of the above embodiments, the present invention is further illustrated by the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by mass.
Example 1
The embodiment provides a preparation method of an ultrafine lithium vanadium phosphate nano microcrystal integrated chip, which comprises the following steps:
1) Preparing graphene oxide into a solution A according to a ratio of 8: 2:3 to prepare a solution B, stirring the solution A and the solution B at 20 ℃, performing ultrasonic treatment for 30min, adding 30 percent by weight of oxalic acid, and performing freeze drying to obtain lithium vanadium phosphate precursor powder;
2) Sintering lithium vanadium phosphate precursor powder for 10 hours at 800 ℃ under the argon condition to obtain a superfine nano lithium vanadium phosphate nano microcrystal material;
3) According to the lithium vanadium phosphate microcrystalline material: acetylene black: PVDF is 8.
The superfine lithium vanadium phosphate nano microcrystal integrated chip prepared in the embodiment 1 is taken as an example for carrying out appearance and structure characterization, and a result graph shown in a figure 1-3 is obtained.
Fig. 1 is a TEM image of the lithium vanadium phosphate nanocrystalline material, and it can be seen from fig. 1 that lithium vanadium phosphate particles in the lithium vanadium phosphate nanocrystalline material are uniformly dispersed on the graphene sheet layer, and the particle size of the lithium vanadium phosphate material is about 5nm.
Fig. 2 is an SEM image of the lithium vanadium phosphate nanocrystalline material, and it can be seen from fig. 2 that many tiny lithium vanadium phosphate nanocrystals form a sheet shape, and the microscopic morphology is excellent, indicating that the lithium vanadium phosphate nanocrystalline-removing integrated sheet is successfully prepared.
Fig. 3 is an XPS diagram of the lithium vanadium phosphate nanocrystalline material, and as can be seen from fig. 3, the key elements and valence states in the lithium vanadium phosphate prove that the obtained lithium vanadium phosphate material is obtained.
The button type lithium ion full cell obtained by assembling the superfine lithium vanadium phosphate nano microcrystal integrated sheet and the graphite cathode electrode sheet is tested for specific capacity-voltage curves at 1 circle, 50 circles, 100 circles, 150 circles, 200 circles and 300 circles within the voltage range of 2.7-4.3V to obtain a result graph shown in figure 4, as can be seen from figure 4, a voltage platform is stable during charging and discharging, after 300 circles are circulated, the specific discharge capacity is 125.6mAh/g, and the superfine lithium vanadium phosphate nano microcrystal integrated sheet electrode sheet and the corresponding cell have better performances.
Example 2
The embodiment provides a preparation method of an ultrafine lithium vanadium phosphate nano microcrystal integrated chip, which comprises the following steps:
1) Preparing graphene oxide into a solution A according to the proportion of 8: 2:4 to obtain solution B, stirring the solution A and B at 20 deg.C, performing ultrasonic treatment for 30min, adding oxalic acid 30 wt%, and freeze drying to obtain lithium vanadium phosphate precursor powder;
2) Sintering lithium vanadium phosphate precursor powder for 10 hours at 800 ℃ under the argon condition to obtain a superfine nano lithium vanadium phosphate nano microcrystal material;
3) According to the lithium vanadium phosphate microcrystalline material: acetylene black: PVDF is 8.
Example 3
The embodiment provides a preparation method of an ultrafine lithium vanadium phosphate nanocrystalline integrated chip, which comprises the following steps:
1) Preparing graphene oxide into a solution A according to a ratio of 8:1: 3 to prepare a solution B, stirring the solution A and the solution B at 20 ℃, performing ultrasonic treatment for 30min, adding 30 percent by weight of oxalic acid, and performing freeze drying to obtain lithium vanadium phosphate precursor powder;
2) Sintering lithium vanadium phosphate precursor powder for 10 hours at 800 ℃ under the argon condition to obtain a lithium vanadium phosphate nano microcrystal material with superfine nano size;
3) According to the lithium vanadium phosphate microcrystalline material: acetylene black: PVDF is 8.
Example 4
The embodiment provides a preparation method of an ultrafine lithium vanadium phosphate nanocrystalline integrated chip, which comprises the following steps:
1) Preparing graphene oxide into a solution A according to a ratio of 8:1: 2 to prepare solution B, stirring the solution A and the solution B at 30 ℃, performing ultrasonic treatment for 40min, adding 30 percent by weight of oxalic acid, and performing freeze drying to obtain lithium vanadium phosphate precursor powder;
2) Sintering lithium vanadium phosphate precursor powder for 20 hours at 1000 ℃ under the argon condition to obtain a lithium vanadium phosphate nano microcrystal material with superfine nano size;
3) According to the lithium vanadium phosphate microcrystalline material: acetylene black: PVDF is 7.
Example 5
The embodiment provides a preparation method of an ultrafine lithium vanadium phosphate nano microcrystal integrated chip, which comprises the following steps:
1) Preparing graphene oxide into a solution A according to a proportion of 7:2: 5 to obtain solution B, stirring the solution A and B at 25 deg.C, performing ultrasonic treatment for 40min, adding oxalic acid 30 wt%, and freeze drying to obtain lithium vanadium phosphate precursor powder;
2) Sintering lithium vanadium phosphate precursor powder for 24 hours at 800 ℃ under the argon condition to obtain a lithium vanadium phosphate nano microcrystal material with superfine nano size;
3) According to the lithium vanadium phosphate microcrystalline material: acetylene black: PVDF is 3.
Although the present disclosure has been described with reference to the above embodiments, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (10)
1. The preparation method of the superfine lithium vanadium phosphate nano microcrystal integrated chip is characterized by comprising the following steps:
s1, preparing graphene oxide, a vanadium source, a lithium source and a phosphorus source into a mixed solution, adding a reducing agent into the mixed solution after ultrasonic stirring, and freeze-drying after reaction to obtain lithium vanadium phosphate precursor powder;
s2, sintering the lithium vanadium phosphate precursor powder under a protective atmosphere to obtain a lithium vanadium phosphate nano microcrystal material;
and S3, mixing the lithium vanadium phosphate nano microcrystal material, a conductive additive, a binder and an organic solvent to prepare electrode slurry, coating the electrode slurry on a current collector, and drying to obtain the superfine lithium vanadium phosphate nano microcrystal integrated sheet.
2. The production method according to claim 1, wherein in step S1, the mass ratio of the graphene oxide, the vanadium source, the lithium source, the phosphorus source, and the oxalic acid is (0.1-1): (3-5): (1-2): (3-5): (0.5-1.5).
3. The method of claim 1 or 2, wherein the vanadium source comprises vanadium pentoxide or ammonium metavanadate, the lithium source comprises one of lithium carbonate, lithium oxalate and lithium nitrate, the phosphorus source comprises phosphoric acid, and the reducing agent comprises oxalic acid or acetic acid.
4. The method of claim 3, wherein the ultrasonic agitation is carried out at a temperature of 10 to 30 ℃ for a period of 30 to 60min.
5. The method according to claim 1, wherein in step S2, the sintering temperature is 200-500 ℃, the holding time is 1-5h, and the heating rate is 2-10 ℃ for min -1 。
6. The preparation method according to claim 1, wherein in step S3, the mass ratio of the lithium vanadium phosphate nanocrystalline material, the conductive additive and the binder is (5-8): (1-4).
7. The preparation method according to claim 6, wherein the conductive additive is acetylene black, the binder is polyvinylidene fluoride (PVDF), the organic solvent is ethanol or N-methylpyrrolidone, and the current collector comprises aluminum foil.
8. An ultra-fine lithium vanadium phosphate nano-microcrystal integrated chip is characterized by being prepared by the preparation method of the ultra-fine lithium vanadium phosphate nano-microcrystal integrated chip disclosed by any one of claims 1 to 7.
9. The integrated ultrafine lithium vanadium phosphate nanocrystallines according to claim 8, wherein the integrated ultrafine lithium vanadium phosphate nanocrystallines comprise a current collector and an electrode layer coated on the surface of the current collector, and the thickness of the electrode layer is in the range of 10 to 300 μm.
10. The application of the ultra-fine lithium vanadium phosphate nano-crystallite integrated sheet as claimed in claim 8 or 9 in the field of lithium ion batteries.
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