CN116177612B - Lithium ion battery positive electrode material and preparation method thereof, and lithium ion battery and preparation method thereof - Google Patents
Lithium ion battery positive electrode material and preparation method thereof, and lithium ion battery and preparation method thereof Download PDFInfo
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- CN116177612B CN116177612B CN202310125166.5A CN202310125166A CN116177612B CN 116177612 B CN116177612 B CN 116177612B CN 202310125166 A CN202310125166 A CN 202310125166A CN 116177612 B CN116177612 B CN 116177612B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000007774 positive electrode material Substances 0.000 title claims description 24
- 239000010405 anode material Substances 0.000 claims abstract description 42
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000013225 prussian blue Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 21
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229960003351 prussian blue Drugs 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 11
- 238000005303 weighing Methods 0.000 claims abstract description 10
- 238000011068 loading method Methods 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- 239000003792 electrolyte Substances 0.000 claims description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 229910052786 argon Inorganic materials 0.000 claims description 19
- 239000004743 Polypropylene Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000011267 electrode slurry Substances 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 239000003273 ketjen black Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 4
- 238000005524 ceramic coating Methods 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
- 239000011261 inert gas Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 36
- 238000012360 testing method Methods 0.000 description 24
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 8
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 8
- 229910013553 LiNO Inorganic materials 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000007581 slurry coating method Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009423 ventilation 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
- H01M4/13—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
-
- 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
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/12—Sulfides
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- 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
- H01M4/58—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- 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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- 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
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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
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Abstract
The invention discloses a lithium ion battery anode material and a preparation method thereof, wherein the preparation method comprises the following steps: s1, weighing Prussian blue powder with a certain mass, loading the Prussian blue powder into an alumina crucible, and placing the alumina crucible into a tube furnace; s2, introducing inert gas into the tube furnace for a certain time; and step S3, under the heating condition, introducing inert gas and carbon disulfide gas into the tube furnace, performing heat treatment on the Prussian blue powder, and preserving heat for a certain time to obtain the Fe 7S8 lithium ion battery anode material. The lithium ion battery anode material provided by the invention has the advantages of good conductivity and insignificant volume expansion effect. The invention also discloses a lithium ion battery and a preparation method thereof, and the lithium ion battery prepared based on the lithium ion battery anode material has good battery cycle performance and stability. Meanwhile, the preparation method has simple process flow and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery positive electrode material and a preparation method thereof, and a lithium ion battery and a preparation method thereof.
Background
Environmental pollution and energy crisis have become two major challenges facing humans. Accordingly, efforts have been made to develop green innovative technologies that seek to address durable energy storage applications. The lithium ion battery is widely used in the energy storage field due to the characteristics of high energy density, small volume, safety and the like.
The iron-based sulfide is widely studied as an electrode material of a lithium ion battery due to the characteristics of high theoretical specific capacity, environmental friendliness, rich reserves and the like. The theoretical capacity of the composite material Fe 7S8 with mixed valence state and inherent metal characteristic is 661mAh/g, which is far higher than that of a commercial graphite electrode material. However, the problems of serious volume expansion, poor conductivity, multiple side reactions and the like of Fe 7S8 limit the wide application of the Fe 7S8 in batteries. In order to solve the above problems, the existing method generally designs a nano structure, which can relieve volume expansion, release stress and shorten ion transmission distance, or designs a core-shell structure, which is compounded with a carbon material, and the core-shell structure can adapt to volume change, so that the carbon material improves conductivity and further improves electrochemical performance. However, the modification method has complex process flow and high cost, and is difficult to adapt to industrial large-scale application.
Disclosure of Invention
In view of the above, the present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a lithium ion battery anode material and a preparation method thereof, and a lithium ion battery and a preparation method thereof. The lithium ion battery anode material provided by the invention has the advantages of good conductivity and insignificant volume expansion effect. The lithium ion battery prepared based on the lithium ion battery anode material has good battery cycle performance and stability. Meanwhile, the preparation method has simple process flow and is suitable for large-scale industrial production.
To this end, in a first aspect, an embodiment of the present invention provides a method for preparing a positive electrode material of a lithium ion battery, where the method includes: s1, weighing Prussian blue powder with a certain mass, loading the Prussian blue powder into an alumina crucible, and placing the alumina crucible into a tube furnace; step S2, argon is introduced into the tube furnace for 30 minutes so as to completely exhaust air in the tube furnace; and step S3, introducing argon gas and carbon disulfide gas into the tubular furnace under the heating condition, and performing heat treatment on the Prussian blue powder, wherein the argon flow is 50-100ml/min during the heat treatment, the heat treatment temperature is 500-1000 ℃, the heat treatment time is 6-12 h, the heat preservation temperature is 500-1000 ℃ and the heat preservation time is 6-10 h, so that the Fe 7S8 lithium ion battery anode material can be obtained.
In a second aspect, an embodiment of the present invention provides a lithium ion battery positive electrode material prepared by using the preparation method of the lithium ion battery positive electrode material provided in the first aspect.
In a third aspect, an embodiment of the present invention provides a lithium ion battery, including a positive electrode sheet containing the positive electrode material for a lithium ion battery described in the second aspect, a separator located between the positive electrode sheet and the negative electrode sheet, and an electrolyte.
In a fourth aspect, an embodiment of the present invention provides a method for preparing the lithium ion battery provided in the third aspect, where the preparation method includes: s4, weighing the Fe 7S8 lithium ion battery anode material, the conductive carbon black and the binder according to a certain mass ratio, stirring for a certain time, and mixing to prepare electrode slurry; step S5, coating the electrode slurry on an aluminum foil, drying for a certain time, putting the aluminum foil into a vacuum drying oven for drying, and cutting to obtain a positive plate; and S6, assembling the positive plate, the negative plate, the diaphragm and the electrolyte to obtain the lithium ion battery.
Preferably, in step S4, the mass ratio of the Fe 7S8 lithium ion battery positive electrode material, the conductive carbon black, and the binder is 8:1:1.
Preferably, in step S4, the conductive carbon black is Ketjen black ECP-600JD, the binder is polyvinylidene fluoride, and the stirring time is 1h.
Preferably, in step S5, the drying time is 8-12 hours, and the vacuum drying time is 12-24 hours.
Preferably, in step S6, the separator is one or more of a PP (polypropylene) single-layer separator, a ceramic coating separator, and a PP-PE-PP (polypropylene-polyethylene-polypropylene) three-layer separator, and the electrolyte is one or more of an ester electrolyte and an ether electrolyte.
The lithium ion battery anode material and the preparation method thereof provided by the embodiment of the invention have a nano-network structure, so that the purpose of inhibiting the volume expansion of the Fe 7S8 lithium ion battery anode material is achieved. Meanwhile, the Fe 7S8 lithium ion battery anode material provided by the embodiment of the invention has a three-dimensional network structure, is connected through the high-conductivity carbon nano tube, is favorable for electronic conduction, and improves the electrochemical performance of the Fe 7S8 lithium ion battery anode material. In addition, the lithium ion battery formed by taking the lithium ion battery anode material prepared by the method as a raw material has higher specific discharge capacity and good cycling stability, and has wide development prospect.
Drawings
Fig. 1 is a schematic diagram of a preparation method of a positive electrode material of a lithium ion battery according to an embodiment of the present invention.
Fig. 2 is a flowchart of a preparation method of a positive electrode material of a lithium ion battery according to an embodiment of the present invention.
Fig. 3 is a flowchart of a method for preparing a lithium ion battery according to an embodiment of the present invention.
Fig. 4 is an XRD characterization diagram of the positive electrode material of the Fe 7S8 lithium ion battery provided in example 1 of the present invention.
Fig. 5 is a scanning electron microscope morphology diagram of the Fe 7S8 lithium ion battery cathode material provided in embodiment 1 of the present invention.
Fig. 6 is a TEM characterization diagram of the Fe 7S8 lithium ion battery positive electrode material provided in example 1 of the present invention.
Fig. 7 is a graph showing test cycle and capacity performance results of half cells of the compositions of examples 1 and 2 of the present invention in an ester electrolyte (1.0M LiPF6 inEC:DEC =1:1 vol%) and an ether electrolyte (1.0M LiTFSI in DME:DOL = 1:1Vol%with 1.0%LiNO 3), respectively;
FIG. 8 is a graph showing the cycle and capacity performance results for half cells of the compositions of examples 2 and 3 of the present invention under 0.1C test conditions;
FIG. 9 is a graph showing the cycle and capacity performance results for half cells of the present invention consisting of examples 2 and 3 under 1C test conditions;
fig. 10 is a graph showing the results of testing the rate performance of half cells composed of examples 2 and 3 according to the present invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The following disclosure provides many different embodiments, or examples, for implementing different structures of the invention. In order to simplify the present disclosure, components and arrangements of specific examples are described below. They are, of course, merely examples and are not intended to limit the invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art will recognize the applicability of other processes and/or the use of other materials.
Referring to fig. 1, an embodiment of the present invention provides a positive electrode material for a lithium ion battery and a preparation method thereof, which are used for preparing a positive electrode material for a lithium ion battery with good conductivity and insignificant volume expansion effect, wherein the positive electrode material for a lithium ion battery is a positive electrode material for a Fe 7S8 lithium ion battery. The lithium ion battery prepared based on the lithium ion battery anode material has good battery cycle performance and stability. As shown in fig. 2, the preparation method of the positive electrode material of the lithium ion battery comprises the following steps:
s1, weighing Prussian blue powder with a certain mass, loading the Prussian blue powder into an alumina crucible, and placing the alumina crucible into a tube furnace;
Wherein the chemical formula of Prussian blue is Fe 4[Fe(CN)6]3.
S2, introducing inert gas into the tube furnace for a certain time;
The inert gas in the embodiment of the invention can be argon, and the ventilation time is 30 minutes, so that the air in the tube furnace is completely discharged.
And step S3, under the heating condition, introducing inert gas and carbon disulfide gas into the tube furnace, performing heat treatment on the Prussian blue powder, and preserving heat for a certain time to obtain the Fe 7S8 lithium ion battery anode material.
Wherein the inert gas can be argon, the flow of the argon is 50-100ml/min during heat treatment, the heat treatment temperature can be 500-1000 ℃, the heat treatment time is 6-12 h, the heat preservation temperature can be 500-1000 ℃, and the heat preservation time is 6-10 h.
It will be appreciated that in order to eliminate off-gas from the tube furnace, the embodiment of the invention is connected to a treatment vessel at the rear end of the tube furnace, wherein the treatment vessel is filled with sodium hydroxide solution for absorbing unreacted carbon disulphide gas.
According to the lithium ion battery anode material prepared by the preparation method of the lithium ion battery anode material provided by the embodiment of the invention, argon carrying carbon disulfide gas is introduced into the tubular furnace, so that a sulfur source is provided after the carbon disulfide is decomposed at high temperature, and the sulfur source reacts with Prussian blue (Fe 4[Fe(CN)6]3) in the tubular furnace to form the carbon layer coated Fe 7S8 lithium ion battery anode material. The Fe 7S8 lithium ion battery anode material has a nano-network structure, so that the purpose of inhibiting the volume expansion of the Fe 7S8 lithium ion battery anode material is achieved. Meanwhile, the Fe 7S8 lithium ion battery anode material provided by the embodiment of the invention has a three-dimensional network structure, is connected through the high-conductivity carbon nano tube, is favorable for electronic conduction, and improves the electrochemical performance of the Fe 7S8 lithium ion battery anode material.
The second aspect of the embodiment of the invention also provides a lithium ion battery and a preparation method thereof, the lithium ion battery comprises a positive plate, a negative plate, a diaphragm positioned between the positive plate and the negative plate and electrolyte, and the positive plate contains the Fe 7S8 lithium ion battery positive electrode material provided by the first aspect of the embodiment of the invention. As shown in fig. 3, the preparation method of the lithium ion battery comprises the following steps:
And S4, weighing the Fe 7S8 lithium ion battery anode material, the conductive carbon black and the binder according to a certain mass ratio, and stirring and mixing for a certain time to prepare the electrode slurry.
Wherein, the mass ratio of the Fe 7S8 lithium ion battery anode material to the conductive carbon black to the binder is 8:1:1. the conductive carbon black can be Ketjen black ECP-600JD, the adhesive can be polyvinylidene fluoride, and the stirring time can be 1h.
And S5, coating the electrode slurry on an aluminum foil, drying for a certain time, putting into a vacuum drying oven for drying, and cutting to obtain the positive plate.
Wherein, the drying time can be 8-12h, and the vacuum drying time can be 12-24h.
And S6, assembling the positive plate, the negative plate, the diaphragm and the electrolyte to obtain the lithium ion battery.
Wherein, the diaphragm can be one or more of a PP (polypropylene) single-layer diaphragm, a ceramic coating diaphragm and a PP-PE-PP (polypropylene-polyethylene-polypropylene) three-layer diaphragm. The electrolyte may be one or more of an ester electrolyte (1.0MLiPF6 in EC:DEC =1:1 vol%), an ether electrolyte (1.0M LiTFSI in DME:DOL =1:1 vol% with1.0% lino 3).
According to the lithium ion battery prepared by the preparation method of the lithium ion battery provided by the embodiment of the invention, the positive plate is prepared by utilizing the Fe 7S8 lithium ion battery positive electrode material, so that the volume expansion phenomenon of the Fe 7S8 lithium ion battery positive electrode material is relieved in the battery cycle process, the side reaction is inhibited, and the structural stability of the lithium ion battery is further improved. Meanwhile, the preparation method has simple process flow and is suitable for large-scale industrial production.
The following describes the specific process and effects of the preparation method of the positive electrode material for a lithium ion battery and the preparation method of the lithium ion battery according to the present invention in detail with reference to some specific examples, but is not limited to the scope of protection of the present invention.
Unless otherwise specified, the chemical reagents and materials in the present invention are all commercially available.
Example 1
The embodiment provides a lithium ion battery anode material and a preparation method of a lithium ion battery, comprising the following steps:
weighing 2g of Prussian blue powder, putting the powder into an alumina crucible, and putting a sample into a tube furnace;
Argon is introduced into the tube furnace for 30min;
Heating the tubular furnace to 900 ℃ at a heating rate of 5 ℃/min, introducing argon and carbon disulfide gas into the tubular furnace, performing heat treatment on the Prussian blue powder, and preserving heat for 6 hours at 900 ℃ to obtain the Fe 7S8 lithium ion battery anode material;
Grinding and mixing Fe 7S8 lithium ion battery anode material, ketjen black ECP-600JD conductive carbon black for 45min, then adding polyvinylidene fluoride binder, and stirring for 1h to prepare electrode slurry, wherein the mass ratio of the Fe 7S8 lithium ion battery anode material to the Ketjen black ECP-600JD conductive carbon black to the polyvinylidene fluoride binder is 8:1:1, a step of;
Coating the electrode slurry coating machine to the rough surface of the aluminum foil, wherein the coating thickness is 200um; heating and qualifying on a coating machine, fixing a coated pole piece on a glass plate, and drying in a blast drying box for 12 hours; cutting the dried coated pole piece into a wafer with the diameter of 12mm, and putting the wafer into a vacuum drying oven to be dried for 24 hours at the temperature of 100 ℃ to obtain a dried positive pole piece;
And assembling the positive plate, the negative plate, the diaphragm and the ester electrolyte (1.0M LiPF6 in EC:DEC =1:1 vol%) to obtain the lithium ion battery.
The XRD characterization pattern of the Fe 7S8 lithium ion battery positive electrode material prepared according to example 1 is shown in fig. 4.
A scanning electron microscope morphology diagram of the Fe 7S8 lithium ion battery anode material prepared according to example 1 is shown in FIG. 5.
A TEM characterization of the Fe 7S8 lithium ion battery cathode material prepared according to example 1 is shown in fig. 6.
Example 2
The embodiment provides a lithium ion battery anode material and a preparation method of a lithium ion battery, comprising the following steps:
weighing 2g of Prussian blue powder, putting the powder into an alumina crucible, and putting a sample into a tube furnace;
Argon is introduced into the tube furnace for 30min;
Heating the tubular furnace to 900 ℃ at a heating rate of 5 ℃/min, introducing argon and carbon disulfide gas into the tubular furnace, performing heat treatment on the Prussian blue powder, and preserving heat for 6 hours at 900 ℃ to obtain the Fe 7S8 lithium ion battery anode material;
Grinding and mixing Fe 7S8 lithium ion battery anode material, ketjen black ECP-600JD conductive carbon black for 45min, then adding polyvinylidene fluoride binder, and stirring for 1h to prepare electrode slurry, wherein the mass ratio of the Fe7S8 lithium ion battery anode material to the Ketjen black ECP-600JD conductive carbon black to the polyvinylidene fluoride binder is 8:1:1, a step of;
Coating the electrode slurry coating machine to the rough surface of the aluminum foil, wherein the coating thickness is 200um; heating and qualifying on a coating machine, fixing a coated pole piece on a glass plate, and drying in a blast drying box for 12 hours; cutting the dried coated pole piece into a wafer with the diameter of 12mm, and putting the wafer into a vacuum drying oven to be dried for 24 hours at the temperature of 100 ℃ to obtain a dried positive pole piece;
And assembling the positive plate with a negative plate, a diaphragm and an ether electrolyte (1.0M LiTFSI in DME:DOL = 1:1Vol%with 1.0%LiNO 3) to obtain the lithium ion battery.
Example 3
The embodiment provides a lithium ion battery anode material and a preparation method of a lithium ion battery, comprising the following steps:
weighing 2g of Prussian blue powder, putting the powder into an alumina crucible, and putting a sample into a tube furnace;
Argon is introduced into the tube furnace for 30min;
Heating the tubular furnace to 500 ℃ at a heating rate of 5 ℃/min, introducing argon and carbon disulfide gas into the tubular furnace, performing heat treatment on the Prussian blue powder, and preserving heat for 6 hours at 500 ℃ to obtain the Fe7S8 lithium ion battery anode material;
Grinding and mixing Fe 7S8 lithium ion battery anode material, ketjen black ECP-600JD conductive carbon black for 45min, then adding polyvinylidene fluoride binder, and stirring for 1h to prepare electrode slurry, wherein the mass ratio of the Fe 7S8 lithium ion battery anode material to the Ketjen black ECP-600JD conductive carbon black to the polyvinylidene fluoride binder is 8:1:1, a step of;
Coating the electrode slurry coating machine to the rough surface of the aluminum foil, wherein the coating thickness is 200um; heating and qualifying on a coating machine, fixing a coated pole piece on a glass plate, and drying in a blast drying box for 12 hours; cutting the dried coated pole piece into a wafer with the diameter of 12mm, and putting the wafer into a vacuum drying oven to be dried for 24 hours at the temperature of 100 ℃ to obtain a dried positive pole piece;
And assembling the positive plate with a negative plate, a diaphragm and an ether electrolyte (1.0M LiTFSI in DME:DOL = 1:1Vol%with 1.0%LiNO 3) to obtain the lithium ion battery.
The products prepared in examples 1-3 above were subjected to performance tests, including the following:
(1) Different electrolyte circulation and capacity tests were performed as follows:
In an argon glove box, a negative electrode case, a spring sheet, a gasket, a lithium sheet (d=14 mm), 15uL of an ester electrolyte (1.0M LiPF6 in EC:DEC =1:1 vol%), a common separator (PP-PE-PP), 35uL of an ester electrolyte (1.0M LiPF6 in EC:DEC =1:1 vol%), and the positive electrode sheet, gasket, and electrode case obtained in example 1 were assembled into half cells in this order.
In an argon glove box, a negative electrode case, a spring sheet, a gasket, a lithium sheet (d=14 mm), a 15uL ether electrolyte (1.0M LiTFSI in DME:DOL = 1:1Vol%with 1.0%LiNO 3), a normal separator (PP-PE-PP), a 35uL ether electrolyte (1.0M LiTFSI in DME:DOL = 1:1Vol%with 1.0%LiNO 3), the positive electrode sheet obtained in example 2, the gasket, and the electrode case were assembled into a half cell in this order.
The assembled half cell of example 1 and the assembled half cell of example 2 were cycled and capacity tested in ether and ester electrolytes at 5C and a cut-off voltage of 1.1-2.6V, respectively, on a blue cell testing apparatus. The results of the battery cycling and capacity testing in the different electrolytes are shown in fig. 7.
(2) Different heat treatment temperature cycles and capacity tests were carried out as follows:
The testing method comprises the following steps:
in an argon glove box, a negative electrode case, a spring sheet, a gasket, a lithium sheet (d=14 mm), a 15uL ether electrolyte (1.0M LiTFSI in DME:DOL = 1:1Vol%with 1.0%LiNO 3), a normal separator (PP-PE-PP), a 35uL ether electrolyte (1.0M LiTFSI in DME:DOL = 1:1Vol%with 1.0%LiNO 3), the positive electrode sheets, gaskets, and electrode cases obtained in example 2 and example 3 were assembled into half batteries in this order.
The half-cell assembled in example 2 and the half-cell assembled in example 3 were respectively subjected to cycle and capacity tests on blue battery test equipment at 0.1C, 1C, and cut-off voltages of 1.1 to 2.6V, and to rate tests at 0.1C, 0.2C, 0.5C, 1C, 2C, and 4C, and cut-off voltages of 1.1 to 2.6V. The results of the cycle and capacity tests at the different heat treatment temperatures under the 0.1C test conditions are shown in fig. 8, the results of the cycle and capacity tests at the different heat treatment temperatures under the 1C test conditions are shown in fig. 9, and the results of the rate performance tests are shown in fig. 10.
From the above examples and the comparison of the test results obtained from testing them, the following conclusions can be drawn:
(1) In the ester electrolyte, the initial specific discharge capacity of the example 1 is 222.8mAh g -1 under the 5C test condition, and in the ether electrolyte, the initial specific discharge capacity of the example 2 is 324.4mAh g -1 under the 5C test condition, and after 400 cycles, the discharge capacity still has 323.8mAh g -1 and is basically not attenuated.
(2) Example 3 the heat treatment temperature was 500 ℃, the initial specific discharge capacity was 455.9mAh g -1 under 0.1C test conditions and 344.7mAh g -1 under 1C test conditions in an ether electrolyte. Example 2 the heat treatment temperature was 900 ℃, the initial specific discharge capacity was 492.3mAh g -1 under the test condition of 0.1C in ether electrolyte, the initial specific discharge capacity was 422.1mAh g -1 under the test condition of 1C, and after 2000 cycles, the discharge capacity was still 298.3mAh g -1 with a per-cycle decay rate of 0.015%.
In conclusion, the lithium ion battery anode material and the lithium ion battery provided by the embodiment of the invention have excellent multiplying power performance and cycle stability, and have wide prospect. Meanwhile, the preparation method has simple process flow and is suitable for large-scale industrial production.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., 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 present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment 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. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.
Claims (8)
1. The preparation method of the lithium ion battery anode material is characterized by comprising the following steps:
s1, weighing Prussian blue powder with a certain mass, loading the Prussian blue powder into an alumina crucible, and placing the alumina crucible into a tube furnace;
Step S2, argon is introduced into the tube furnace for 30 minutes so as to completely exhaust air in the tube furnace;
And step S3, introducing argon and carbon disulfide gas into the tubular furnace under the heating condition, and performing heat treatment on the Prussian blue powder, wherein the flow of the argon is 50-100ml/min during the heat treatment, the heat treatment temperature is 500-1000 ℃, the heat treatment time is 6-12 h, the heat preservation temperature is 500-1000 ℃ and the heat preservation time is 6-10 h, so that the Fe 7S8 lithium ion battery anode material can be obtained.
2. A lithium ion battery cathode material, characterized in that the lithium ion battery cathode material is applied with a preparation method comprising the lithium ion battery cathode material according to claim 1.
3. The utility model provides a lithium ion battery, includes positive plate, negative plate, is located diaphragm and electrolyte between positive plate and the negative plate, its characterized in that: the positive electrode sheet comprises the positive electrode material of the lithium ion battery as claimed in claim 2.
4. A method of making the lithium-ion battery of claim 3, comprising:
s4, weighing the Fe 7S8 lithium ion battery anode material, the conductive carbon black and the binder according to a certain mass ratio, stirring for a certain time, and mixing to prepare electrode slurry;
step S5, coating the electrode slurry on an aluminum foil, drying for a certain time, putting the aluminum foil into a vacuum drying oven for drying, and cutting to obtain a positive plate;
and S6, assembling the positive plate, the negative plate, the diaphragm and the electrolyte to obtain the lithium ion battery.
5. The method according to claim 4, wherein in step S4, the mass ratio of the Fe 7S8 lithium ion battery positive electrode material, the conductive carbon black, and the binder is 8:1:1.
6. The method according to claim 4, wherein in the step S4, the conductive carbon black is Ketjen black ECP-600JD, the binder is polyvinylidene fluoride, and the stirring time is 1h.
7. The method according to claim 4, wherein in step S5, the drying time is 8-12 hours, and the vacuum drying time is 12-24 hours.
8. The method according to claim 4, wherein in step S6, the separator is one or more of a PP (polypropylene) single-layer separator, a ceramic coating separator, and a PP-PE-PP (polypropylene-polyethylene-polypropylene) three-layer separator, and the electrolyte is one or more of an ester electrolyte and an ether electrolyte.
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