CN114149032A - Nano-hierarchical nickel cobaltous oxide material, preparation method thereof, semi-solid dual-ion battery anode slurry and semi-solid dual-ion battery - Google Patents
Nano-hierarchical nickel cobaltous oxide material, preparation method thereof, semi-solid dual-ion battery anode slurry and semi-solid dual-ion battery Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 71
- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000007787 solid Substances 0.000 title claims abstract description 46
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 title claims abstract description 26
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000006256 anode slurry Substances 0.000 title claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000006258 conductive agent Substances 0.000 claims abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 27
- 239000002105 nanoparticle Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 11
- 150000001868 cobalt Chemical class 0.000 claims description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002057 nanoflower Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011267 electrode slurry Substances 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 150000002500 ions Chemical class 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 abstract description 6
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 5
- 238000010298 pulverizing process Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract description 2
- 238000010923 batch production Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- 239000011244 liquid electrolyte Substances 0.000 description 6
- 229910001425 magnesium ion Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 4
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910019400 Mg—Li Inorganic materials 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- -1 compound magnesium chloride-aluminum chloride-magnesium chloride Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- 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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- 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
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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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 provides a nano hierarchical structure nickel cobaltous oxide material, a preparation method thereof, semi-solid double-ion battery anode slurry and a semi-solid double-ion battery. Firstly, nickel cobaltate with a nano hierarchical structure is obtained by a hydrothermal method, and then the nickel cobaltate with the nano hierarchical structure is further obtained by thermal reaction with sodium sulfide nonahydrate. After being uniformly ground and mixed, the nickel thiocobalate active material and the conductive agent are dispersed in a diionic electrolyte formed by a holophenyl complex (APC) added with lithium bistrifluoromethanesulfonylimide, and stirred to form semi-solid slurry with certain viscoelasticity and rheological property, wherein the slurry has the properties of ion transmission and electron conduction. The semi-solid dual-ion battery assembled based on the slurry can effectively promote high-speed transmission of electricity/ions through a three-dimensional mixed conductive network, relieves the problem of electrode material pulverization and shedding, and has good circulation stability. And the synthesis process is simple, the requirements on experimental instruments and equipment are low, the raw materials are easy to obtain, the cost is low, and batch production can be carried out.
Description
Technical Field
The invention belongs to the technical field of new energy storage, and relates to a nano hierarchical structure nickel cobaltous oxide material and a preparation method thereof, a semi-solid dual-ion battery based on the nano hierarchical structure nickel cobaltous oxide material and a preparation method thereof, and an assembled semi-solid dual-ion battery.
Disclosure of Invention
Since the new century, the problem of energy shortage is increasingly prominent, and a more suitable novel energy storage device is urgently needed to be researched; lithium ion batteries using all-liquid electrolytes are a new type of electric energy storage equipment developed since the late 20 th century, and have been widely used in various commercial and consumer energy storage fields due to their advantages of low self-discharge, wide working temperature range, environmental protection, and the like.
However, the traditional lithium ion battery based on the full liquid electrolyte has the problems that the electrode material is easy to be pulverized and fall off after long-term circulation, potential safety hazards are caused by lithium dendrites and the like, so that the development of the lithium ion battery with long service life and high capacity is greatly limited. Therefore, the magnesium battery with low cost, high natural abundance and high safety has better development prospect, the pure magnesium ion battery has low energy density, the electrochemical system is difficult to be effectively activated, and the double-ion battery combining the dendrite-free magnesium metal cathode and the lithium embeddable anode with rapid kinetic reaction has unique advantages in constructing the energy storage system with high safety and high energy density.
However, the magnesium-lithium dual-ion battery based on the all-liquid electrolyte has the problems of low overall energy density caused by limited solid content of the load of the dry pole piece, electrode breakage caused by the fact that stress cannot be released due to volume structure change in the charging and discharging process and the like, and is not favorable for exerting the energy storage characteristic.
In order to solve the above technical problems, an object of the present invention is to provide a nano-sized nickel cobaltous oxide material and a method for preparing the same, which can solve the problem of volume expansion of the conventional battery material, and accelerate electron ion transport to obtain high capacity and fast charging performance.
The invention also aims to provide semi-solid dual-ion battery anode slurry, which is prepared based on a nano hierarchical structure nickel cobaltous oxide material, solves the problems of electrode pulverization, cracking and the like in the traditional full-liquid electrolyte battery, and enhances the cycle stability and the cycle life of the battery.
The invention also aims to provide a semi-solid dual-ion battery, which is prepared by using the semi-solid dual-ion battery anode slurry.
The specific technical scheme of the invention is as follows:
a preparation method of a nano hierarchical structure nickel cobaltothioate material comprises the following steps:
1) mixing cobalt salt, nickel salt and urea in water, adding ammonium fluoride after mixing, stirring and uniformly mixing to obtain a mixed solution, and carrying out hydrothermal reaction;
2) placing the product obtained in the step 1) in an air atmosphere for annealing and roasting to obtain nickel cobaltate;
3) mixing the nickel cobaltate treated in the step 2) and a sulfur source in water, stirring and uniformly mixing to obtain a mixed solution, and carrying out hydrothermal reaction to obtain the nano hierarchical nickel cobaltate material.
In the step 1), the mass ratio of the nickel salt to the cobalt salt is 1: 2;
in the step 1), the cobalt salt is soluble cobalt salt, preferably cobalt nitrate hexahydrate;
in the step 1), the nickel salt is soluble nickel salt, preferably nickel nitrate hexahydrate;
in the step 1), the quantity ratio of the cobalt salt to the urea substance is 1:4-1: 7;
in the step 1), the mass ratio of the cobalt salt to the ammonium fluoride is 1:1-1: 3;
the concentration of the cobalt salt in the mixed solution is 0.05 mol/L;
in the step 1), the hydrothermal reaction temperature is 90-150 ℃, preferably 110-130 ℃; the reaction time is 2 to 6 hours, preferably 3 to 4 hours;
after the reaction in the step 1) is finished, washing, drying and collecting a product; and then step 2) is performed.
Drying in step 1), wherein the drying temperature is 40-80 ℃, and preferably 50-60 ℃; the drying time is 4 to 12 hours, preferably 6 to 8 hours.
Step 2) roasting refers to: the roasting temperature is 350-450 ℃, preferably 400-450 ℃, and the roasting time is 2-4 hours, preferably 2-3 hours.
In the step 3), the mass ratio of the nickel cobaltate to the sulfur source is 1:2-1:7, preferably 1:3-1: 5;
the sulfur source in the step 3) is sodium sulfide nonahydrate;
the dosage ratio of the sulfur source to the water in the step 3) is 0.03-0.1 mol/L;
in the step 3), the hydrothermal reaction temperature is 100-140 ℃, and preferably 110-130 ℃; the reaction time is 6 to 10 hours, preferably 7 to 9 hours.
After the reaction in the step 3) is finished, washing, drying and collecting a product;
the drying temperature in the step 3) is 40-80 ℃, preferably 50-60 ℃; the drying time is 4 to 12 hours, preferably 6 to 8 hours.
The water used in the present invention is deionized water.
The invention provides a nano hierarchical structure nickel cobaltosic acid material which is prepared by adopting the method. The nickel cobaltous oxide material with the nano hierarchical structure grows nickel cobaltous oxide with a radial three-dimensional array structure on a nano flower.
The semisolid dual-ion battery anode slurry provided by the invention is prepared by utilizing the nano hierarchical structure nickel thiocobalate material.
The preparation method of the semi-solid state double-ion battery anode slurry comprises the following steps:
A. dispersing lithium salt in the all-phenyl complex to form a double-ion electrolyte;
B. uniformly grinding and mixing the nano hierarchical nickel cobaltous oxide material and the conductive agent, and stirring and dispersing the mixture in the double-ion electrolyte to form semi-solid slurry with rheological property.
In the step A, the lithium salt is dispersed in the all-phenyl complex and is continuously stirred for 8-12 hours at the rotating speed of 800-.
In the step A, the concentrations of magnesium ions and lithium ions in the electrolyte are the same, and the concentration of the lithium ions in the electrolyte is 0.2-0.5mol/L, preferably 0.4 mol/L.
In the step A, the lithium salt is bis (trifluoromethane sulfonyl) imide lithium;
in the step A, the preparation method of the all-phenyl complex comprises the following steps: dissolving and dispersing anhydrous aluminum chloride in an anhydrous tetrahydrofuran solvent, continuously stirring for 8-12h at 800-1500 r/min, adding anhydrous phenylmagnesium chloride, and continuously stirring for 8-12h at 800-1500 r/min to obtain the aluminum chloride.
The holophenyl complex is called APC for short;
the dosage ratio of the anhydrous aluminum chloride to the anhydrous tetrahydrofuran solvent is 0.6-0.7 mol/L.
The dosage ratio of the anhydrous aluminum chloride to the anhydrous phenylmagnesium chloride is 1 mol/L;
the mass ratio of the nano hierarchical structure nickel cobaltosic acid material to the conductive agent in the step B is 8:1-4: 1;
the conductive agent in the step B is conductive carbon black;
in the step B, the mass ratio range of the mass of the nano hierarchical structure nickel cobaltous oxide material and the conductive agent to the mass of the double-ion electrolyte is 1:3-1:7, preferably 1:4-1: 6;
stirring in the step B, wherein the stirring speed range is 500-1200 r/min, preferably 600-1000 r/min;
stirring in step B for a period of time in the range of 0.5 to 6 hours, preferably 0.5 to 4 hours.
The semisolid dual-ion battery provided by the invention is prepared by utilizing the semisolid dual-ion battery anode slurry.
And (3) assembling the semi-solid dual-ion battery anode slurry prepared in the above step into a button battery (CR2032 type): coating 20-40mg of the prepared semi-solid state double-ion battery anode slurry on a wafer copper foil with the diameter of 12mm, wherein pure magnesium metal is used as a counter electrode, and a glass fiber separator is used as a diaphragm; the magnesium negative electrode was supplemented with 40-80 μ l of the diionic electrolyte prepared in accordance with the present invention and the cell was assembled in a glove box (Mikrouna, Super (1220/750/900)) filled with pure argon.
According to the traditional lithium ion battery based on the full liquid electrolyte, after long-term circulation, the electrode material is easy to pulverize and fall off, lithium dendrite can bring potential safety hazards and other problems, so that the reliability is poor, the safety is reduced, the defects are difficult to effectively solve under the full liquid electrolyte system, and the application of the lithium ion battery with long service life and high stability is greatly limited. Therefore, the research on the novel semi-solid battery is of great significance.
The present invention relates to a nano-sized hierarchical structure material for improving the agglomeration problem and the contact resistance problem of an active material in a semi-solid battery. The hydrothermal preparation method is simple and convenient, the morphology of the material is easy to regulate, and the invention grows the radial three-dimensional array on the nanoflower to form a unique novel nanomaterial. The reasonably designed nano hierarchical structure is beneficial to mutual contact between nano materials, accelerates electron transmission and reduces contact resistance; the nano flower-like structure also has a large specific surface area and can load more active substances. In addition, the hierarchical structure can promote electricity/ion transmission, reduce the loss of active mass in the discharging/charging process, and relieve the volume expansion of the material, thereby improving the electrochemical stability of the battery.
The invention prepares a nickel thiocobalate material NiCo with a nano hierarchical structure2S4Firstly adding nickel salt, cobalt salt and urea, then adding ammonium fluoride, using nickel source and cobalt source to combine them to produce nickel cobaltate, using urea as precipitant, slowly decomposing under the condition of hydrothermal reaction and releasing CO2And NH3With simultaneous hydrolysis to CO3 2-And OH-The anion and the ammonium fluoride cooperate to regulate and form a uniform nano hierarchical structure. The post-addition of ammonium fluoride facilitates the formation of the final hierarchical morphology. According to the invention, nickel cobaltate with a nano hierarchical structure is obtained by a hydrothermal method, and then the nickel cobaltate with the nano hierarchical structure is further obtained by a thermal reaction with sodium sulfide nonahydrate.
When the semisolid dual-ion battery positive electrode slurry is prepared, a nickel cobaltous oxide material with a nano hierarchical structure and a conductive agent are uniformly ground and mixed, and then are dispersed in a dual-ion electrolyte formed by an all-phenyl complex (APC) added with bis (trifluoromethane sulfonyl imide) lithium, and the semi-solid slurry with certain viscoelasticity and rheological property is formed by stirring, and has the properties of ion transmission and electron conduction. The semi-solid dual-ion battery assembled based on the slurry can effectively promote high-speed transmission of electricity/ions through a three-dimensional mixed conductive network, relieves the problem of electrode material pulverization and shedding, and has good circulation stability.
In magnesium-based electrolyte, compared with oxide, the existence of sulfide can reduce the polarity of magnesium ions and improve the ion intercalation rate; in the circulating process of the electrolyte, the surface of the magnesium cathode is easily covered and passivated by insoluble magnesium chloride with low ionic conductivity, and the lithium salt is added into the electrolyte, so that the dissolution of the magnesium chloride on the surface of the magnesium cathode can be promoted, the effects of activating the electrolyte/cathode interface and reducing the magnesium deposition-dissolution overpotential are achieved; in addition, the addition of the lithium salt reduces the interface reaction resistance, accelerates the continuous kinetic conversion process of ion transmission, realizes high-efficiency magnesium-lithium co-intercalation of the nickel cobaltous oxide and greatly improves the energy density.
Compared with the prior art, the invention has the following advantages: a radial three-dimensional array grows on the nickel cobaltous oxide nanoflower prepared by a hydrothermal method and is in a nano hierarchical structure; the prepared nickel cobaltosic oxide nano material has stable performance, is not easy to denature in air and is easy to store; the prepared nickel cobaltous oxide nano hierarchical structure has large specific surface area and is beneficial to effective contact with ions; the semi-solid slurry formed by mixing the nickel cobaltate and the electrolyte has an elastic rheological conductive network, so that the pulverization and the falling of the electrode material are prevented while the conductivity is improved. The prepared active slurry is used as the positive electrode of the semi-solid magnesium-lithium double-ion battery, and has large capacity, good cycle stability and high safety; the synthesis process is simple, the requirements on experimental instruments and equipment are low, raw materials are easy to obtain, the cost is low, and batch production can be carried out.
Drawings
FIG. 1 is an SEM image of nano-sized hierarchical nickel cobaltothiocate prepared in example 1;
FIG. 2 is an SEM image of nano-sized hierarchical nickel cobaltothiocate prepared in example 2;
FIG. 3 is an SEM image of nano-sized hierarchical nickel cobaltothiocate prepared in example 3;
FIG. 4 is an enlarged SEM image of nano-sized hierarchically structured nickel thiocobalate prepared in example 2;
FIG. 5 is a TEM image of nano-sized hierarchically structured nickel thiocobalate prepared in example 2;
FIG. 6 is an XRD pattern of a nano-sized hierarchical nickel cobaltous oxide material prepared in example 2;
FIG. 7 is a semi-solid slurry rheology display picture of the nano-sized hierarchical nickel thiocobalate material prepared in example 2 mixed with a bi-ionic electrolyte;
FIG. 8 is a graph showing the cycling stability of the semi-solid magnesium-lithium bi-ion battery prepared in example 2 at current densities of 20mA/g and 100 mA/g;
FIG. 9 is a graph of the charge of semi-solid Mg-Li bi-ion battery prepared in example 2 at 20mA/g and 100mA/g current density for the 10 th cycle;
fig. 10 is an SEM image of the nano-sized nickel cobaltate material prepared in example 2.
Detailed Description
Example 1
A preparation method of a nano hierarchical structure nickel cobaltothioate material comprises the following steps:
1) 0.4362g of nickel nitrate hexahydrate, 0.8731g of cobalt nitrate hexahydrate and 0.72g of urea are dissolved in 60ml of deionized water, stirring is carried out for 30 minutes, 0.111g of ammonium fluoride is added, stirring is continued for 5 minutes, then the mixed solution is transferred into a reaction kettle, hydrothermal reaction is carried out for 2 hours at 100 ℃, precipitates are collected, washing is carried out, and drying is carried out for 6 hours at 60 ℃ to obtain the product.
2) Roasting the product prepared in the step 1) for 2 hours at 350 ℃ in the air atmosphere, and then naturally cooling to obtain a nickel cobaltate material with a nano hierarchical structure;
3) and (3) dissolving 0.2g of the nickel cobaltate material obtained in the step 2) and 0.6g of sodium sulfide nonahydrate in 60ml of deionized water, stirring for 30 minutes, transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction at 100 ℃ for 6 hours, collecting precipitates, washing, and drying at 60 ℃ for 12 hours to obtain the product.
The SEM image of the nano-sized hierarchical nickel cobaltothiocarbonate prepared in example 1 is shown in FIG. 1;
a semi-solid double-ion battery anode slurry is prepared by using the nickel cobaltous oxide material with a nano hierarchical structure in the embodiment 1, and the specific preparation method comprises the following steps:
A. dispersing lithium bis (trifluoromethanesulfonyl) imide in an all-phenyl complex (APC) at room temperature, and continuously stirring for 12 hours at 1000 r/min to form a double-ion electrolyte with the concentrations of lithium ions and magnesium ions both being 0.4 mol/L;
the preparation method of the all-phenyl complex comprises the following steps: dissolving and dispersing 0.666g of anhydrous aluminum chloride in 7.5ml of anhydrous tetrahydrofuran solvent, stirring at a high speed of 1000 r/min for 8 hours, adding 5ml of anhydrous phenylmagnesium chloride into the solution, and stirring at 1000 r/min for 8 hours to obtain the compound magnesium chloride-aluminum chloride-magnesium chloride solution;
B. uniformly grinding and mixing 0.08g of the nano-sized hierarchical nickel cobaltous oxide material prepared in the embodiment 1 and 0.02g of conductive carbon black, stirring and dispersing the mixture in 0.4g of the double-ion electrolyte prepared in the step A at 800 revolutions per minute for 0.5 hour to form semi-solid slurry with rheological property;
C. and D, assembling the semi-solid slurry prepared in the step B into the semi-solid dual-ion battery.
Example 2
A preparation method of a nano hierarchical structure nickel cobaltothioate material comprises the following steps:
1) 0.4362g of nickel nitrate hexahydrate, 0.8731g of cobalt nitrate hexahydrate and 1.081g of urea are dissolved in 60ml of deionized water, stirred for 30 minutes, then 0.2593g of ammonium fluoride is added, stirring is continued for 5 minutes, then the mixed solution is transferred into a reaction kettle, hydrothermal reaction is carried out for 3 hours at 120 ℃, precipitates are collected, washed, and dried for 8 hours at 60 ℃, and the product is obtained.
2) Roasting the product prepared in the step 1) for 2 hours at 400 ℃ in the air atmosphere, and then naturally cooling to obtain a nickel cobaltate material with a nano hierarchical structure;
3) and (2) dissolving 0.2g of the nickel cobaltate material obtained in the step 2) and 0.8g of sodium sulfide nonahydrate in 60ml of deionized water, stirring for 30 minutes, transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 8 hours, collecting precipitates, washing, and drying at 60 ℃ for 12 hours to obtain the product nickel thiocobalate material with the nano hierarchical structure.
The SEM image of the nano-sized hierarchical nickel cobaltothiocarbonate prepared in example 2 is shown in FIG. 2; the enlarged view is shown in FIG. 4, and the TEM image is shown in FIG. 5; the XRD pattern is shown in figure 6.
A semi-solid double-ion battery anode slurry is prepared by using the nickel cobaltous oxide material with the nano hierarchical structure in the embodiment 2, and the specific preparation method comprises the following steps:
A. dispersing lithium bis (trifluoromethanesulfonyl) imide in an all-phenyl complex (APC), and continuously stirring for 12 hours at 1000 revolutions per minute to form a double-ion electrolyte with the concentration of 0.4mol/L, wherein lithium ions and magnesium ions are both formed; the preparation of the said per-phenyl complex is as in example 1.
B. Uniformly grinding and mixing 0.08g of the nano-sized nickel cobaltous oxide material prepared in the embodiment 2 and 0.02g of conductive carbon black, and stirring and dispersing the mixture in 0.5g of the double-ion electrolyte prepared in the step A for 1 hour at 800 revolutions per minute to form semi-solid slurry with rheological property;
C. and D, assembling the semi-solid slurry prepared in the step B into a semi-solid dual-ion battery, and specifically assembling into a button battery (CR2032 type): and coating 30mg of the formed semi-solid slurry on a wafer copper foil with the diameter of 12mm, wherein pure magnesium metal is used as a counter electrode, and a glass fiber separator is used as a diaphragm. And the magnesium cathode is supplemented with 50 mu L of the double-ion electrolyte prepared in the step A. All batteries were cycled over a potential range of 0.01-2.0V by a constant current charge/discharge method on a novice battery tester with the results shown in fig. 8, 9, having a specific discharge capacity of 324mAh/g after 10 cycles at a current density of 20mA/g and 140mAh/g after 10 cycles at a current density of 100 mA/g.
Example 3
A preparation method of a nano hierarchical structure nickel cobaltothioate material comprises the following steps:
1) 0.4362g of nickel nitrate hexahydrate, 0.8731g of cobalt nitrate hexahydrate and 1.081g of urea are dissolved in 60ml of deionized water, stirred for 30 minutes, then 0.2593g of ammonium fluoride is added, stirring is continued for 5 minutes, then the mixed solution is transferred into a reaction kettle, hydrothermal reaction is carried out for 4 hours at 120 ℃, precipitates are collected, washed and dried for 6 hours at 60 ℃, and the product is obtained.
2) Roasting the product prepared in the step 1) for 2 hours at 450 ℃ in the air atmosphere, and then naturally cooling to obtain a nickel cobaltate material with a nano hierarchical structure;
3) and (2) dissolving 0.2g of the nickel cobaltate material obtained in the step 2) and 1.4g of sodium sulfide nonahydrate in 60ml of deionized water, stirring for 30 minutes, transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 10 hours, collecting precipitates, washing, and drying at 60 ℃ for 12 hours to obtain the product nickel thiocobalate material with the nano hierarchical structure.
The SEM image of the nano-sized hierarchical nickel cobaltothiocate prepared in example 3 is shown in FIG. 3.
A semi-solid double-ion battery anode slurry is prepared by using the nickel cobaltous oxide material with a nano hierarchical structure in the embodiment 3, and the specific preparation method comprises the following steps:
A. dispersing lithium bis (trifluoromethanesulfonyl) imide in an all-phenyl complex (APC) at room temperature, and continuously stirring at 900 revolutions per minute for 12 hours to form a double-ion electrolyte with the concentrations of lithium ions and magnesium ions both being 0.4 mol/L; the procedure for the preparation of the said per-phenyl complex (APC) is as in example 1.
B. Uniformly grinding and mixing 0.08g of the nano-sized nickel cobaltous oxide material prepared in the embodiment 1 and 0.02g of conductive carbon black, and stirring and dispersing the mixture in 0.6g of the double-ion electrolyte prepared in the step A for 2 hours at 800 r/min to form semi-solid slurry with rheological property;
6) and (4) assembling the semi-solid slurry prepared in the step 5) into a semi-solid dual-ion battery.
Claims (10)
1. A preparation method of a nano hierarchical structure nickel cobaltothioate material is characterized by comprising the following steps:
1) mixing cobalt salt, nickel salt and urea in water, adding ammonium fluoride after mixing, stirring and uniformly mixing to obtain a mixed solution, and carrying out hydrothermal reaction;
2) placing the product obtained in the step 1) in an air atmosphere for annealing and roasting to obtain nickel cobaltate;
3) mixing the nickel cobaltate treated in the step 2) and a sulfur source in water, stirring and uniformly mixing to obtain a mixed solution, and carrying out hydrothermal reaction to obtain the nano hierarchical nickel cobaltate material.
2. The method according to claim 1, wherein in step 1), the ratio of the amount of the nickel salt to the cobalt salt is 1: 2.
3. The method according to claim 1 or 2, wherein the hydrothermal reaction temperature in step 1) is 90 ℃ to 150 ℃ and the reaction time is 2 to 6 hours.
4. The method according to claim 1, wherein the firing of step 2) is: the roasting temperature is 350-450 ℃, and the roasting time is 2-4 hours.
5. The method according to claim 1, wherein in step 3), the mass ratio of the nickel cobaltate to the sulfur source is in the range of 1:2 to 1: 7.
6. The method as claimed in claim 1, wherein the hydrothermal reaction temperature in step 3) is 100-140 ℃ and the reaction time is 6-10 hours.
7. A nano-sized hierarchical structure nickel cobaltous oxide material prepared by the preparation method of any one of claims 1 to 6, wherein the nano-sized hierarchical structure nickel cobaltous oxide material is prepared by growing radial three-dimensional array structure nickel cobaltous oxide on nanoflowers.
8. A semi-solid double-ion battery anode slurry is characterized by being prepared by using the nickel thiocobalate material with the nano hierarchical structure of claim 5; the preparation method of the semi-solid state double-ion battery anode slurry comprises the following steps:
A. dispersing lithium salt in the all-phenyl complex to form a double-ion electrolyte;
B. uniformly grinding and mixing the nano hierarchical nickel cobaltous oxide material and the conductive agent, and stirring and dispersing the mixture in the double-ion electrolyte to form semi-solid slurry with rheological property.
9. The semi-solid state bi-ion battery positive electrode slurry of claim 6, wherein in step a, the lithium salt is lithium bistrifluoromethanesulfonylimide.
10. A semi-solid bi-ion battery prepared by using the semi-solid bi-ion battery positive electrode slurry of claim 8 or 9.
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