CN114149032B - Nano hierarchical structure nickel thiocobalt material, preparation method thereof, semi-solid double-ion battery anode slurry and semi-solid double-ion battery - Google Patents
Nano hierarchical structure nickel thiocobalt material, preparation method thereof, semi-solid double-ion battery anode slurry and semi-solid double-ion battery Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 75
- 239000007787 solid Substances 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000006256 anode slurry Substances 0.000 title claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000006258 conductive agent Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000002105 nanoparticle 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
- 239000002057 nanoflower Substances 0.000 claims description 5
- 239000011267 electrode slurry Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims 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 claims description 3
- 238000000137 annealing Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 13
- 230000005540 biological transmission Effects 0.000 abstract description 8
- 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
- 238000000227 grinding Methods 0.000 abstract description 4
- 238000010298 pulverizing process Methods 0.000 abstract description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 230000005611 electricity Effects 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
- 238000006243 chemical reaction 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
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 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
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 5
- 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002086 nanomaterial Substances 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
- 238000005406 washing Methods 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000009977 dual effect Effects 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
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000013049 sediment 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 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
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 239000002253 acid Substances 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
- 229910052786 argon Inorganic materials 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
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 239000012467 final product Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
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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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- 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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- C01—INORGANIC CHEMISTRY
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- 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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- 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
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01—INORGANIC CHEMISTRY
- 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
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Abstract
The invention provides a nickel thiocobalt material with a nano hierarchical structure, a preparation method thereof, semi-solid double-ion battery anode slurry and semi-solid double-ion battery. Firstly, nickel cobaltate with a nano hierarchical structure is obtained through a hydrothermal method, and then the nickel cobaltate sulfide material with the nano hierarchical structure is further obtained through a hydrothermal reaction with sodium sulfide nonahydrate. After uniformly grinding and mixing a nickel thiocobalt active material and a conductive agent, dispersing the nickel thiocobalt active material and the conductive agent in a double-ion electrolyte formed by a full phenyl complex (APC) added with lithium bistrifluoromethane sulfonyl imide, and stirring 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 double-ion battery assembled based on the slurry can effectively promote high-speed transmission of electricity/ions through a three-dimensional mixed conductive network, alleviate the problem of pulverization and falling of electrode materials, and has good circulation stability. And the synthesis process is simple, the requirement on experimental instruments and equipment is low, 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 nickel thiocobalt material and a preparation method thereof, a semi-solid double-ion battery based on the nano hierarchical nickel thiocobalt material and a preparation method thereof, and an assembled semi-solid double-ion battery.
Disclosure of Invention
Since the new century, the problem of energy shortage is increasingly prominent, and research on a more suitable novel energy storage device is urgently needed; lithium ion batteries using all-liquid electrolytes are novel electric energy storage devices developed from 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 operating temperature range, green environmental protection, etc.
However, the traditional lithium ion battery based on the full-liquid electrolyte has the problems that electrode materials are 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 long-life high-capacity lithium ion battery is greatly limited. Therefore, the magnesium battery with low cost, high natural abundance and high safety has more development prospect, the pure magnesium ion battery has low energy density and is difficult to be activated effectively by an electrochemical system, and the double ion battery combining the dendrite-free magnesium metal negative electrode and the lithium-intercalated positive electrode with rapid dynamic reaction has unique advantages in constructing an 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 that the whole energy density is low due to limited load solid content of the dry pole piece, and the electrode is broken due to the fact that stress cannot be released due to volume structure change in the charging and discharging process, and the like, so that the energy storage characteristic is not beneficial to exerting.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a nickel thiocobalt material with a nano hierarchical structure and a preparation method thereof, which solve the problem of volume expansion of the traditional battery material and accelerate the transmission of electronic ions to obtain high capacity and quick charge performance.
The invention also aims to provide the semi-solid double-ion battery anode slurry, which is prepared based on the nano hierarchical structure nickel thiocobalt material, solves the problems of electrode pulverization and 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 the semi-solid double-ion battery, which is prepared by using the positive electrode slurry of the semi-solid double-ion battery.
The specific technical scheme of the invention is as follows:
the preparation method of the nickel thiocobalt material with the nano hierarchical structure comprises the following steps:
1) Mixing cobalt salt, nickel salt and urea in water, adding ammonium fluoride after mixing, stirring and uniformly mixing, and performing hydrothermal reaction on the obtained mixed solution;
2) Annealing and roasting the product obtained in the step 1) in an air atmosphere to obtain nickel cobaltate;
3) Mixing the nickel cobaltate and the sulfur source treated in the step 2) in water, stirring and uniformly mixing to obtain a mixed solution, and performing hydrothermal reaction to obtain the nickel cobaltate material with the nano hierarchical structure.
In step 1), the ratio of the amount of nickel salt to cobalt salt is 1:2;
in step 1), the cobalt salt is a soluble cobalt salt, preferably cobalt nitrate hexahydrate;
in step 1), the nickel salt is a soluble nickel salt, preferably nickel nitrate hexahydrate;
in step 1), the ratio of the cobalt salt to the urea substance is 1:4 to 1:7;
in the step 1), the 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 0.05mol/L;
in step 1), the hydrothermal reaction temperature is 90 ℃ to 150 ℃, preferably 110 ℃ to 130 ℃; the reaction time is 2 to 6 hours, preferably 3 to 4 hours;
after the reaction in the step 1), washing, drying and collecting the product; and step 2) is carried out again.
Drying in step 1) at a drying temperature of 40 ℃ to 80 ℃, preferably 50 ℃ to 60 ℃; the drying time is 4 to 12 hours, preferably 6 to 8 hours.
Step 2) the roasting refers to: the calcination temperature is 350-450 ℃, preferably 400-450 ℃, and the calcination time is 2-4 hours, preferably 2-3 hours.
In step 3), the mass ratio of the nickel cobaltate to the sulfur source is in the range of 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 0.03-0.1mol/L;
in step 3), the hydrothermal reaction temperature is 100-140 ℃, preferably 110-130 ℃; the reaction time is from 6 to 10 hours, preferably from 7 to 9 hours.
After the reaction in the step 3), washing, drying and collecting the product;
the drying temperature in step 3) is 40 ℃ to 80 ℃, preferably 50 ℃ to 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 nickel thiocobalt material with the nano hierarchical structure is prepared by adopting the method. The nano hierarchical structure nickel thiocobalt material grows nickel thiocobalt with radial three-dimensional array structure on the nano flower.
The semi-solid double-ion battery anode slurry provided by the invention is prepared from the nickel thiocobalt material with the nano hierarchical structure.
The preparation method of the semi-solid double-ion battery anode slurry comprises the following steps:
A. dispersing lithium salt in the full phenyl complex to form a double-ion electrolyte;
B. the nano hierarchical structure nickel thiocobalt material and the conductive agent are uniformly ground and mixed, and then stirred and dispersed in the double-ion electrolyte to form semi-solid slurry with rheological property.
In the step A, lithium salt is dispersed in the full phenyl complex, and stirring is carried out continuously for 8-12 hours at the rotating speed of 800-1500 rpm, so as to obtain the double-ion electrolyte.
In the step A, the concentration of magnesium ions and lithium ions in the electrolyte is the same, and the concentration of lithium ions in the electrolyte is 0.2-0.5mol/L, preferably 0.4mol/L.
In the step A, the lithium salt is lithium bis (trifluoromethanesulfonyl) imide;
in the step A, the preparation method of the full phenyl complex comprises the following steps: dissolving and dispersing anhydrous aluminum chloride in anhydrous tetrahydrofuran solvent, continuously stirring for 8-12h at 800-1500 rpm, adding anhydrous phenyl magnesium chloride, and continuously stirring for 8-12h at 800-1500 rpm.
The full phenyl complex is called APC for short;
the dosage ratio of the anhydrous aluminum chloride to the anhydrous tetrahydrofuran solvent is 0.6-0.7mol/L.
The dosage ratio of the anhydrous aluminum chloride to the anhydrous phenyl magnesium chloride is 1mol/L;
the mass ratio of the nickel thiocobalt material with the nano hierarchical structure 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 of the nano hierarchical structure nickel thiocobalt material to the conductive agent to the mass ratio of the double-ion electrolyte is 1:3-1:7, preferably 1:4-1:6;
the stirring in the step B is carried out at a stirring speed ranging from 500 to 1200 revolutions per minute, preferably from 600 to 1000 revolutions per minute;
the stirring in step B is carried out for a period of time in the range from 0.5 to 6 hours, preferably from 0.5 to 4 hours.
The semi-solid double-ion battery provided by the invention is prepared from the positive electrode slurry of the semi-solid double-ion battery.
Taking the prepared semi-solid double-ion battery anode slurry, assembling the semi-solid double-ion battery, and specifically assembling the semi-solid double-ion battery into a button battery (CR 2032 type): 20-40mg of the prepared semi-solid double-ion battery anode slurry is coated on a copper foil with a diameter of 12mm, 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 μl of the prepared dual ion electrolyte, and the cell was assembled in a glove box (Mikrouna, super (1220/750/900)) filled with pure argon.
The traditional lithium ion battery based on the full-liquid electrolyte has the problems that the electrode material is easy to pulverize and fall off after long-term circulation, potential safety hazards are caused by lithium dendrites, and the like, 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 of the novel semi-solid battery is of great significance.
In order to improve the agglomeration problem and the contact resistance problem of active materials in a semi-solid battery, the invention designs a nano hierarchical structure material. The hydrothermal preparation method is simple and convenient, the morphology of the material is easy to regulate, and the radial three-dimensional array grows on the nanoflower to form a unique novel nanomaterial. The nano hierarchical structure with reasonable design is beneficial to the mutual contact between nano materials, accelerates the electron transmission and reduces the contact resistance; the nano flower-like structure also has large specific surface area and can load more active substances. In addition, the hierarchical structure can promote electric/ion transmission, reduce active mass loss in the discharging/charging process, and relieve volume expansion of materials, so that electrochemical stability of the battery is improved.
The invention prepares nickel thiocobalt material NiCo with nano hierarchical structure 2 S 4 When the method is used, firstly, nickel salt, cobalt salt and urea are added, then ammonium fluoride is added, a nickel source and a cobalt source are used for combining to generate nickel cobaltate, urea is taken as a precipitator, and CO is slowly decomposed under the hydrothermal condition to release 2 And NH 3 Simultaneously hydrolyzing to generate CO 3 2- And OH (OH) - Anions, in cooperation with ammonium fluoride, 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, the nickel cobaltate with the nano hierarchical structure is obtained by a hydrothermal method, and then the nickel cobaltate sulfide material with the nano hierarchical structure is further obtained by a hydrothermal reaction with sodium sulfide nonahydrate.
When the semi-solid double-ion battery anode slurry is prepared, nickel thiocobalt material with nano hierarchical structure and conductive agent are uniformly ground and mixed, then dispersed in double-ion electrolyte formed by full phenyl complex (APC) added with lithium bis (trifluoromethane sulfonyl) imide, and the slurry is stirred to form semi-solid slurry with certain viscoelasticity and rheological property, and has the properties of ion transmission and electron conduction. The semi-solid double-ion battery assembled based on the slurry can effectively promote high-speed transmission of electricity/ions through a three-dimensional mixed conductive network, alleviate the problem of pulverization and falling of electrode materials, and has good circulation stability.
In magnesium-based electrolytes, the presence of sulfide reduces the polarity of magnesium ions and increases the rate of ion intercalation compared to oxides; in the process of electrolyte circulation, the surface of the magnesium negative electrode is easily covered by indissolvable magnesium chloride with low ionic conductivity for passivation, and the lithium salt is added into the electrolyte, so that the dissolution of the magnesium chloride on the surface of the magnesium negative electrode can be promoted, the interface of the electrolyte/negative electrode is activated, and the effect of reducing the deposition-dissolution overpotential of the magnesium is achieved; in addition, the addition of lithium salt reduces interface reaction resistance, accelerates continuous kinetic conversion process of ion transmission, enables nickel thiocobalate to realize efficient magnesium-lithium co-intercalation, and greatly improves energy density.
Compared with the prior art, the invention has the following advantages: a radial three-dimensional array grows on the nickel thiocobalt oxide nanoflowers prepared by a hydrothermal method and is in a nano hierarchical structure; the prepared nickel thiocobalate nano material has stable performance, is not easy to be denatured in air and is easy to store; the prepared nickel thiocobalt acid nano-scale structure has large specific surface area, and is beneficial to effective contact with ions; the semi-solid slurry formed by mixing nickel cobaltate and electrolyte has an elastic rheological conductive network, so that the pulverization and the falling off 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 circulation stability and high safety; the synthesis process is simple, the requirement on experimental instruments and equipment is 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 nickel thiocobalt prepared according to example 1;
FIG. 2 is an SEM image of nano-sized nickel thiocobalt prepared according to example 2;
FIG. 3 is an SEM image of nano-sized nickel thiocobalt prepared according to example 3;
FIG. 4 is an enlarged SEM image of the nano-sized nickel thiocobaltate prepared according to example 2;
FIG. 5 is a TEM image of nano-sized nickel thiocobalt prepared in example 2;
FIG. 6 is an XRD pattern of a nano-hierarchical nickel thiocobalt material prepared in example 2;
FIG. 7 is a graph showing the rheological properties of semi-solid slurries formed by mixing a nickel thiocobalt material with a zwitterionic electrolyte in a nano-hierarchical structure prepared in example 2;
FIG. 8 is a graph showing the cyclic stability test of the semi-solid magnesium lithium dual ion battery prepared in example 2 at current densities of 20mA/g and 100 mA/g;
FIG. 9 is a graph showing the charge of the 10 th cycle of the semi-solid magnesium lithium dual ion battery prepared in example 2 at current densities of 20mA/g and 100 mA/g;
fig. 10 is an SEM image of the nano-sized nickel cobaltate material prepared in example 2.
Detailed Description
Example 1
The preparation method of the nickel thiocobalt material with the nano hierarchical structure comprises the following steps:
1) 0.4362g of nickel nitrate hexahydrate, 0.8731g of cobalt nitrate hexahydrate and 0.72g of urea are taken and 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 for hydrothermal reaction for 2 hours at 100 ℃, sediment is collected, washed and dried at 60 ℃ for 6 hours, and the product is obtained.
2) Roasting the product prepared in the step 1) for 2 hours at 350 ℃ in an air atmosphere, and naturally cooling to obtain a nickel cobaltate material with a nano hierarchical structure;
3) 0.2g of the nickel cobaltate material obtained in the step 2) and 0.6g of sodium sulfide nonahydrate are dissolved in 60ml of deionized water, stirred for 30 minutes, then the mixed solution is transferred into a reaction kettle for hydrothermal reaction for 6 hours at 100 ℃, the precipitate is collected, washed and dried for 12 hours at 60 ℃ to obtain the product.
SEM images of the nano-sized nickel thiocobaltate prepared in example 1 are shown in fig. 1;
the semi-solid double-ion battery anode slurry is prepared from the nickel thiocobalt material with the nano hierarchical structure in the embodiment 1, and the specific preparation method comprises the following steps:
A. dispersing lithium bistrifluoromethane sulfonyl imide in a full phenyl complex (APC) at room temperature, and continuously stirring for 12 hours at 1000 revolutions per minute to form a double-ion electrolyte with the concentration of lithium ions and magnesium ions of 0.4 mol/L;
the preparation method of the full phenyl complex comprises the following steps: dissolving and dispersing 0.666g of anhydrous aluminum chloride in 7.5ml of anhydrous tetrahydrofuran solvent, continuously stirring at a high speed of 1000 rpm for 8 hours, adding 5ml of anhydrous phenylmagnesium chloride into the solution, and stirring at a high speed of 1000 rpm for 8 hours to obtain the final product;
B. uniformly grinding and mixing 0.08g of the nano hierarchical nickel thiocobalt material prepared in the example 1 with 0.02g of conductive carbon black, stirring and dispersing the mixture at 800 revolutions per minute in 0.4g of the double-ion electrolyte prepared in the step A for 0.5 hour to form semi-solid slurry with rheological property;
C. and D, taking the semi-solid slurry prepared in the step B, and assembling the semi-solid double-ion battery.
Example 2
The preparation method of the nickel thiocobalt material with the nano hierarchical structure comprises the following steps:
1) 0.4362g of nickel nitrate hexahydrate, 0.8731g of cobalt nitrate hexahydrate and 1.081g of urea are taken and dissolved in 60ml of deionized water, stirring is carried out for 30 minutes, 0.2593g of ammonium fluoride is added, stirring is continued for 5 minutes, then the mixed solution is transferred into a reaction kettle for hydrothermal reaction for 3 hours at 120 ℃, sediment is collected, washed and dried at 60 ℃ for 8 hours, and the product is obtained.
2) Roasting the product prepared in the step 1) for 2 hours at 400 ℃ in an air atmosphere, and naturally cooling to obtain a nickel cobaltate material with a nano hierarchical structure;
3) 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 precipitate, washing, and drying at 60 ℃ for 12 hours to obtain the product nickel cobaltate material with the nano hierarchical structure.
SEM images of the nano-sized nickel thiocobaltate prepared in example 2 are shown in fig. 2; an enlarged view is shown in fig. 4, and a TEM image is shown in fig. 5; the XRD pattern is shown in FIG. 6.
The semi-solid double-ion battery anode slurry is prepared from the nickel thiocobalt material with the nano hierarchical structure in the embodiment 2, and the specific preparation method comprises the following steps:
A. dispersing lithium bistrifluoromethane sulfonyl imide in a full phenyl complex (APC), and continuously stirring for 12 hours at 1000 revolutions per minute to form a double-ion electrolyte with the concentration of lithium ions and magnesium ions of 0.4 mol/L; the preparation method of the full phenyl complex is as in example 1.
B. Uniformly grinding and mixing 0.08g of the nano hierarchical nickel thiocobalt material prepared in the embodiment 2 with 0.02g of conductive carbon black, stirring and dispersing the mixture at 800 revolutions per minute in 0.5g of the double-ion electrolyte prepared in the step A for 1 hour to form semi-solid slurry with rheological property;
C. and B, assembling the semi-solid slurry prepared in the step B into a semi-solid double-ion battery, and specifically assembling into a button battery (CR 2032 type): 30mg of the formed semi-solid slurry was coated on a wafer copper foil of 12mm diameter with pure magnesium metal as a counter electrode and a glass fiber separator as a separator. The magnesium negative electrode was supplemented with 50 μl of the zwitterionic electrolyte prepared in step a. All cells were cycled on a New Wired cell tester by a constant current charge/discharge method over a potential range of 0.01-2.0V as shown in FIGS. 8, 9, with 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
The preparation method of the nickel thiocobalt material with the nano hierarchical structure comprises the following steps:
1) 0.4362g of nickel nitrate hexahydrate, 0.8731g of cobalt nitrate hexahydrate and 1.081g of urea are taken and dissolved in 60ml of deionized water, stirring is carried out for 30 minutes, 0.2593g of ammonium fluoride is added, stirring is continued for 5 minutes, then the mixed solution is transferred into a reaction kettle for hydrothermal reaction for 4 hours at 120 ℃, sediment is collected, washed and dried at 60 ℃ for 6 hours, and the product is obtained.
2) Roasting the product prepared in the step 1) for 2 hours at 450 ℃ in an air atmosphere, and naturally cooling to obtain a nickel cobaltate material with a nano hierarchical structure;
3) 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 precipitate, washing, and drying at 60 ℃ for 12 hours to obtain the product nickel cobaltate material with the nano hierarchical structure.
SEM images of the nano-sized nickel thiocobaltate prepared in example 3 are shown in fig. 3.
The semi-solid double-ion battery anode slurry is prepared from the nickel thiocobalt material with the nano hierarchical structure in the embodiment 3, and the specific preparation method comprises the following steps:
A. dispersing lithium bistrifluoromethane sulfonyl imide in a full phenyl complex (APC) at room temperature, and continuously stirring for 12 hours at 900 revolutions per minute to form a double-ion electrolyte with the concentration of lithium ions and magnesium ions of 0.4 mol/L; the preparation method of the full phenyl complex (APC) is as in example 1.
B. Uniformly grinding and mixing 0.08g of the nano hierarchical nickel thiocobalt material prepared in the embodiment 1 with 0.02g of conductive carbon black, stirring and dispersing the mixture at 800 revolutions per minute in 0.6g of the double-ion electrolyte prepared in the step A for 2 hours to form semi-solid slurry with rheological property;
6) And 5) taking the semi-solid slurry prepared in the step 5), and assembling the semi-solid double-ion battery.
Claims (6)
1. A preparation method of a nickel thiocobalt material with a nano hierarchical structure, which is characterized by comprising the following steps:
1) Mixing cobalt salt, nickel salt and urea in water, stirring for 30 minutes, adding ammonium fluoride after mixing, stirring and uniformly mixing, and performing hydrothermal reaction on the obtained mixed solution;
2) Annealing and roasting the product obtained in the step 1) in an air atmosphere to obtain nickel cobaltate;
3) Mixing the nickel cobaltate treated in the step 2) and a sulfur source in water, stirring uniformly to obtain a mixed solution, and performing hydrothermal reaction to obtain a nickel cobaltate material with a nano hierarchical structure;
in step 1), the ratio of the amount of nickel salt to cobalt salt is 1:2;
in the step 1), the hydrothermal reaction temperature is 90-150 ℃ and the reaction time is 2-6 hours;
in the step 3), the mass ratio of the nickel cobaltate to the sulfur source is in the range of 1:2-1:7;
in the step 3), the hydrothermal reaction temperature is 100-140 ℃ and the reaction time is 6-10 hours;
the nano hierarchical structure nickel thiocobalt material grows nickel thiocobalt with a radial three-dimensional array structure on the nano flower;
the nickel thiocobalt material with the nano hierarchical structure is used for the semi-solid double-ion battery.
2. The method according to claim 1, wherein the firing in step 2) means: the roasting temperature is 350-450 ℃ and the roasting time is 2-4 hours.
3. A nano-sized nickel cobaltate material prepared by the preparation method of claim 1 or 2, wherein the nano-sized nickel cobaltate material grows nickel cobaltate with radial three-dimensional array structure on nanoflower.
4. A semi-solid double-ion battery anode slurry, which is characterized in that the semi-solid double-ion battery anode slurry is prepared by using the nickel thiocobalt material with the nano hierarchical structure according to claim 3; the preparation method of the semi-solid double-ion battery anode slurry comprises the following steps:
A. dispersing lithium salt in the full phenyl complex to form a double-ion electrolyte;
B. the nano hierarchical structure nickel thiocobalt material and the conductive agent are uniformly ground and mixed, and then stirred and dispersed in the double-ion electrolyte to form semi-solid slurry with rheological property.
5. The semi-solid state bi-ionic cell positive electrode slurry according to claim 4, wherein in step a, the lithium salt is lithium bistrifluoromethane sulfonimide.
6. A semi-solid state bi-ionic cell prepared by using the positive electrode slurry of the semi-solid state bi-ionic cell according to claim 4 or 5.
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