CN113851628B - Adhesive-free V 2 O 5 Molten salt electrode material, and preparation method and application thereof - Google Patents
Adhesive-free V 2 O 5 Molten salt electrode material, and preparation method and application thereof Download PDFInfo
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- 150000003839 salts Chemical class 0.000 title claims abstract description 83
- 239000007772 electrode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000002105 nanoparticle Substances 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 241000257465 Echinoidea Species 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- 229910013636 LiCl—LiI Inorganic materials 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 230000009969 flowable effect Effects 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000011345 viscous material Substances 0.000 description 7
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
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- 239000010405 anode material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 238000007780 powder milling Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Chemistry (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an adhesive-free V 2 O 5 A molten salt electrolyte electrode material, a preparation method and application thereof. Adhesive-free V 2 O 5 The molten salt electrolyte electrode material is micro-nano particles, and the particles are formed by sea urchin-like V 2 O 5 The micro-nano particles and molten salt are formed, and the molten salt is in sea urchin shape V 2 O 5 The sea urchin-like structure tightly binds the molten salt that flows easily at high temperature inside the micro-nano particles. The preparation method comprises the following steps: dissolving molten salt in ethanol by heating, and adding sea urchin-like V 2 O 5 The micro-nano particles are stirred until being uniformly mixed to obtain a mixed solution; continuously evaporating ethanol from the obtained mixture under heating to attach molten salt to sea urchin-like V 2 O 5 The micro-nano particles are in the internal gaps; drying the obtained viscous sample under vacuum to obtain adhesive-free V 2 O 5 Molten salt electrode material. The material has good high-temperature discharge performance, good conductivity and stable structure, is used as the positive electrode of the thermal battery, avoids adding inert insulating adhesive, and improves the high-voltage discharge time of the thermal battery.
Description
Technical Field
The invention relates to an adhesive-free V 2 O 5 A preparation method and application of a molten salt electrode, belonging to the technical field of thermal battery anode materials.
Background
The thermal battery is a non-chargeable battery which adopts normal-temperature non-conductive, high-temperature high-conductive molten salt as electrolyte and works in a heat activation mode. The thermal battery has the characteristics of high specific energy and specific power, wide use environment temperature (-50-70 ℃), long storage time (about 20 years), no need of maintenance, quick and reliable activation (less than 0.1 s), compact structure, simple and convenient process, low manufacturing cost, gao Zixuan strong vibration resistance and the like, and is widely applied to the fields of military, underground mining industry and space exploration. Currently, high voltage attenuation of a positive electrode material of a thermal battery is a key problem for limiting the development of the thermal battery, wherein the main problem is the problem of poor conductivity of the positive electrode material.
Transition metal oxide V 2 O 5 The positive electrode material has high specific capacity, high discharge voltage, good thermal stability and air stability, and is considered as one of ideal positive electrode materials of the thermal battery. However, its low conductivity makes its high voltage plateau decay rapidly, and the positive electrode active material utilization is extremely low. To improve V 2 O 5 In general, a certain amount of molten salt electrolyte is added during the preparation of the positive electrode powder. A molten salt electrolyte is an electrolyte material that is solid at normal temperature and is not conductive, but has high fluidity and high ionic conductivity in a high temperature environment. The fluidity of the molten salt is very liable to destroy the structure of the positive electrode. In order to solve the problem of fluidity of molten salt, the adhesive (such as MgO and SiO) with high porosity and high temperature resistance and good compatibility with molten salt is prepared 2 And Al 2 O 3 ) Added to the positive electrode material. The addition of the binder can indeed inhibit the flow of molten salt and improve the structural stability of the positive electrode. However, the process is not limited to the above-described process,for positive electrode active material V 2 O 5 The adhesive is not only an inert material but also an insulating material. The addition of the binder can suppress the flow of molten salt, but also increases the resistance of the positive electrode. This shortens the high voltage discharge time of the battery, i.e., reduces the battery operating life, severely affecting its specific energy and specific power.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide an adhesive-free V 2 O 5 Molten salt electrode material. Increasing V in molten salt 2 O 5 The ionic conductivity is avoided while the influence of the addition of the binder on the conductivity is avoided.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
adhesive-free V 2 O 5 Molten salt electrode material, said adhesive-free form V 2 O 5 The molten salt electrode material is in the form of micro-nano particles, and the particles are formed by molten salt and sea urchin-like V 2 O 5 Micro-nano particles are formed, and molten salt is uniformly embedded into sea urchin-shaped V 2 O 5 The sea urchin-like structure tightly binds the flowable molten salt in the micro-nano particle voids at high temperature.
The molten salts include, but are not limited to, liF-LiCl-LiBr, liCl-KCl, liF-LiCl-LiI, liCl-LiI.
Preferably, the sea urchin shape V 2 O 5 The micro-nano particles are formed by V 2 O 5 Sea urchin balls with macroscopic and micrometer composition of nano particles, V 2 O 5 The nanoparticle size is 20-100nm. Molten salt is filled and adhered to sea urchin-like V 2 O 5 The internal gaps and the surfaces of the micro-nano particles form a single adhesive-free type V 2 O 5 The size of the molten salt electrode material is 10-15 mu m. In addition, the addition of the molten salt electrolyte did not alter sea urchin shape V 2 O 5 Morphology of micro-nano particles. The particulate material of the present invention is therefore in a micro-nano structure.
Preferably, the adhesive-free form V 2 O 5 In the molten salt electrode material, the percentage of molten salt is largeAbout 10% -50%.
The invention also provides the adhesive-free V 2 O 5 A method for preparing a molten salt electrode material comprising the steps of:
(1) Dissolving the pure phase molten salt in ethanol by heating;
(2) Slowly adding sea urchin-like V into the solution in the step (1) 2 O 5 The micro-nano particles are continuously heated and stirred until being uniformly mixed, and a mixed solution is obtained; wherein sea urchin shape V 2 O 5 The mass ratio of the micro-nano particles to the molten salt is 0.3-3.8:0.2;
(3) And (3) rapidly heating and stirring the mixed solution obtained in the step (2) until most of ethanol is evaporated, wherein the mixed solution is sticky.
(4) And (3) drying the viscous mixture obtained in the step (3) in vacuum until no ethanol solvent exists.
Preferably, in step (1) the molten salt is completely dissolved when the ethanol is heated to 50-70 ℃;
preferably, in step (2), stirring is carried out for 2-6 hours.
Preferably, in step (3), the mixture is heated and stirred in a water bath at 70-90 ℃, preferably at 75 ℃.
Preferably, in the step (3), the stirring rate is 100-400r/min.
Preferably, in step (4), the incubation is carried out at 120-180℃for 8-12 hours, preferably 10 hours.
Adhesive-free V according to the invention 2 O 5 Use of a molten salt electrode material in the positive electrode of a thermal battery.
Adhesive-free V according to the invention 2 O 5 The molten salt electrode material may be adhesive-free sea urchin-like V 2 O 5 The molten salt electrode material may be represented by chemical symbol adhesive-free sea urchin shape V 2 O 5 Molten salt.
The preparation method of the composite material comprises the following steps:
(1) Dissolving a certain amount of molten salt into a hot ethanol solution, and keeping the temperature of the hot ethanol at 50-70 ℃;
(2) Stirring the prepared sea urchin-like V 2 O 5 The micro-nano particles are slowly added into hot ethanol solution (sea urchin-like V) 2 O 5 The ratio of the micro-nano particles to the molten salt is 0.3-3.8:0.2);
(3) Stirring to uniformity, rapidly transferring the beaker containing the mixed liquid into equipment with heating and magnetic stirring, and continuously performing thermal stirring until most of ethanol is completely evaporated, wherein the mixture is in a viscous state;
(4) Vacuum air drying the viscous material at 120-180deg.C, and vacuum sealing.
The invention provides a simple solvent method for mixing solid electrolyte in sea urchin shape V 2 O 5 Micro-nano particle method. The prepared adhesive-free sea urchin-shaped V 2 O 5 The molten salt not only adds a certain ionic conductive agent, but also avoids the addition of an adhesive, and is used as a thermal battery anode material, and has the main advantages that:
(1) By virtue of the excellent characteristic that the solid powder of molten salt electrolyte is easily dissolved in ethanol at a certain temperature, the electrolyte powder which is originally in solid state is brought into micro-nano V under the condition of ethanol fluidity 2 O 5 In the void. The method is time-saving, labor-saving, low in cost and capable of mass production.
(2) The use temperature in the preparation process is lower than 200 ℃, and the electrolyte is mixed in ethanol solution, so that the electrolyte is difficult to contact with moisture in the air, and the chemical stability of the electrolyte is better maintained.
(3) The prepared adhesive-free sea urchin-shaped V 2 O 5 Molten salt obtained by using sea urchin-like V alone without using adhesive 2 O 5 The self-structured confinement effect can inhibit the electrolyte which is easy to flow under the high-temperature condition.
(4) Adhesive-free sea urchin shape V 2 O 5 Molten salt having a specific purity of V 2 O 5 Better conductivity.
(5) Adhesive-free sea urchin shape V 2 O 5 The molten salt is used as the positive electrode of the thermal battery, so that the nano effect advantage is achieved, namely the ion conductivity and the reaction completeness of the positive electrode material are improved, and the mass ratio of the positive electrode active material can be improved.
(6) Adhesive-free sea urchin shape V 2 O 5 The molten salt is used as the positive electrode of the thermal battery, so that the structural stability of the positive electrode at high temperature can be maintained, and the structural collapse of the positive electrode caused by electrolyte flow can be prevented.
(7) Adhesive-free sea urchin shape V 2 O 5 The molten salt is used as a positive electrode of a thermal battery, and the addition of a binder is avoided to reduce the ratio and conductivity of the active material.
Drawings
FIG. 1 is an XRD pattern of the powder before and after molten salt addition of example 1.
FIG. 2 shows an adhesive-free sea urchin-like V prepared in example 1 2 O 5 Molten salt and pure phase V 2 O 5 The positive electrode was at 0.1A cm -2 Discharge performance at 500 ℃.
FIG. 3 is a synthetic pure phase sea urchin-like V prepared in example 1 2 O 5 SEM image of micro-nano particles.
FIG. 4 is a diagram of an adhesive-free sea urchin-like V prepared in example 2 2 O 5 SEM image of molten salt electrode material.
FIG. 5 shows an adhesive-free sea urchin-like V prepared in example 3 2 O 5 Molten salt positive electrode and V 2 O 5 Molten salt+MgO positive electrode at 0.1A cm -2 Discharge performance at 500 ℃.
FIG. 6 is a diagram of an adhesive-free sea urchin-like V prepared in example 4 2 O 5 SEM image after positive electrode discharge of molten salt.
Detailed Description
The invention is further illustrated below with reference to examples.
Example 1
First, a certain amount of the molten salt LiF-LiCl-LiBr was mixed into 30ml of ethanol solution, stirred constantly and the temperature was controlled at 50 ℃. Then sea urchin-like V with a particle size of about 10 μm 2 O 5 Micro-nanoThe particles are slowly poured into a hot ethanol solution containing LiF-LiCl-LiBr according to the mass ratio of LiF-LiCl-LiBr of 3:2, and stirred for 2 hours until the mixture is uniform. Then, the stirring and heating temperature was raised to 75 ℃, and the mixture was stirred until most of the ethanol solution in the mixture had evaporated, and the substance was viscous. Finally, drying the viscous substance in a vacuum blowing drying oven at 150 ℃ for 8 hours, and naturally cooling to obtain the adhesive-free sea urchin-shaped V 2 O 5 LiF-LiCl-LiBr electrode material. XRD analysis of the above vacuum dried powder showed that LiF-LiCl-LiBr did not introduce impurity substances nor changed sea urchin-like V 2 O 5 The crystal structure of the nanoparticle. This means that the mixing of this method does not cause sea urchin-like V 2 O 5 Reaction of micro-nano particles with LiF-LiCl-LiBr.
Adhesive-free sea urchin shape V 2 O 5 LiF-LiCl-LiBr positive electrode, liB negative electrode and ternary electrolyte (LiF-LiCl-LiBr/MgO) are matched to prepare a single thermal battery system and the single thermal battery system is 0.1A cm -2 Discharge at-500 deg.C, test result shows that the highest discharge voltage platform is 2.43V, its specific capacity is up to 228mAh g -1 (1.6V at the end, the same applies below) with specific energy of 465.54Wh kg -1 Obviously higher than the sea urchin shape V 2 O 5 Specific capacity 219mAh g when micro-nano particles are positive electrode -1 And specific energy 445.055Wh kg -1 。
Said sea urchin shape V 2 O 5 The micro-nano particles are formed by V 2 O 5 The nano particles are assembled by the following specific method:
1. 3.6g oxalic acid and 0.4g cetyl trimethylammonium bromide were poured into 100ml distilled water and stirred continuously until completely dissolved;
2. pouring 2.34g of sodium metavanadate into the solution, continuously stirring at normal temperature until the color of the solution changes from yellow to orange, and then stirring for 2 hours;
3. transferring the solution to a 200ml polytetrafluoroethylene reaction kettle, heating for 24 hours at 180 ℃, and then cooling to normal temperature;
4. washing the hydro-thermal synthesis sample for three times by water, centrifuging and cleaning, and drying in vacuum at 90 ℃ for 12 hours;
5. and heating the dried sample to 500 ℃ at 3 ℃/min in a tubular furnace under the air environment, preserving heat for 2 hours, naturally cooling to normal temperature, sampling and preserving.
Sea urchin shape V 2 O 5 The micro-nano particle morphology is shown in figure 3, and can be seen that sea urchin shape V 2 O 5 The micro-nano particles are formed by a large amount of V 2 O 5 Micron sea urchin ball-shaped structure formed by stacking nano particles, V 2 O 5 A large number of gaps are formed among the nano particles, and the molten salt is filled in the gaps and cannot cause the sea urchin-shaped V 2 O 5 The overall size of the micro-nano particles is greatly affected. In addition, sea urchin shape V can be regulated by regulating reaction conditions in the preparation process 2 O 5 The micro-nano particle size is controlled between 10 and 15 mu m.
Example 2
First, a certain amount of the molten salt LiF-LiCl-LiBr was mixed into 30ml of ethanol solution, stirred constantly and the temperature was controlled at 60 ℃. Then, sea urchin-like V having a particle size of about 12 μm was obtained 2 O 5 Slowly pouring the mixture into a hot ethanol solution containing LiF-LiCl-LiBr according to the mass ratio of LiF-LiCl-LiBr of 7:3, and stirring for 2h until the mixture is uniformly mixed. Then, the stirring and heating temperature was increased to 80 ℃, and the mixture was stirred until most of the ethanol solution in the mixture had evaporated, and the substance was viscous. Finally, drying the viscous substance in a vacuum forced air drying oven at 160deg.C for 7 hr, and naturally cooling to obtain adhesive-free sea urchin-like V 2 O 5 LiF-LiCl-LiBr electrode material. From adhesive-free sea urchin shape V 2 O 5 As can be seen from SEM image of LiF-LiCl-LiBr (FIG. 4), sea urchin-like V was prepared by liquid phase method 2 O 5 Is uniformly infiltrated into each gap by molten salt LiF-LiCl-LiBr, and is assembled into sea urchin-like V 2 O 5 V of micro-nano particles 2 O 5 The nano particles are adhered to inhibit overflow phenomenon in the discharge process.
Example 3
First, a certain amount of molten salt LiF-LiCl-LiBr is mixedInto 30ml of ethanol solution, stirring was continued and the temperature was controlled at 65 ℃. Then, sea urchin-like V having a particle size of about 15 μm was obtained 2 O 5 The micro-nano particles are slowly poured into a hot ethanol solution containing LiF-LiCl-LiBr according to the mass ratio of the LiF-LiCl-LiBr of 4:1, and stirred for 2.5 hours until the mixture is uniformly mixed. Then, the stirring and heating temperature was raised to 75 ℃, and the mixture was stirred until most of the ethanol solution in the mixture had evaporated, and the substance was viscous. Finally, drying the viscous substance in a vacuum blowing drying oven at 170 ℃ for 7 hours, and naturally cooling to obtain the adhesive-free sea urchin-shaped V 2 O 5 LiF-LiCl-LiBr electrode material. Adhesive-free sea urchin shape V 2 O 5 The LiF-LiCl-LiBr positive electrode shows a specific sea urchin shape V at a discharge temperature of 500 DEG C 2 O 5 The LiF-LiCl-LiBr+MgO cathode (obtained by conventional powder milling technique) has more excellent discharge performance (FIG. 5), and the specific capacity and specific energy are 228mAh g respectively -1 And 465.54Wh kg -1 Is obviously higher than sea urchin shape V 2 O 5 144.759mAh g of LiF-LiCl-LiBr+MgO anode -1 And 260.583Wh kg -1 。
The V is 2 O 5 The preparation method of the LiF-LiCl-LiBr+MgO comprises the following steps: in a vacuum glove box, sea urchin shape V 2 O 5 The micro-nano particles and LiF-LiCl-LiBr+MgO molten salt electrolyte are fully ground and mixed for about 20min, and the sea urchin-shaped V 2 O 5 The mass ratio of the micro-nano particles to LiF-LiCl-LiBr+MgO molten salt electrolyte is 4:1.
example 4
First, a certain amount of the molten salt LiF-LiCl-LiBr was mixed into 30ml of ethanol solution, stirred constantly and the temperature was controlled at 70 ℃. Then sea urchin-like V with a particle size of about 10 μm 2 O 5 Slowly pouring the mixture into a hot ethanol solution containing LiF-LiCl-LiBr according to the mass ratio of the LiF-LiCl-LiBr to the LiF-LiCl-LiBr of 9:1, and stirring the mixture for 2 hours until the mixture is uniformly mixed. Then, the stirring and heating temperature was increased to 90 ℃, and the mixture was stirred until most of the ethanol solution in the mixture had evaporated, and the substance was viscous. Finally, the viscous material is dried in a vacuum blowing drying ovenDrying at 170deg.C for 8 hr, and naturally cooling to obtain adhesive-free sea urchin-like V 2 O 5 LiF-LiCl-LiBr electrode material. As can be seen from the electrode profile after discharge (FIG. 6), there is no adhesive sea urchin shape V 2 O 5 The positive electrode has no obvious holes after the molten salt positive electrode is discharged, which indicates that the sea urchin-shaped V2O5 micro-nano particle structure can well inhibit the fluidity of the molten salt, and more electron transmission channels are provided in the post-discharge process, so that the post-discharge performance is improved.
Example 5
First, a certain amount of molten salt LiCl-KCl was mixed into 30ml of ethanol solution, stirred constantly and the temperature was controlled at 50 ℃. Then sea urchin-like V with a particle size of about 10 μm 2 O 5 The micro-nano particles are slowly poured into a hot ethanol solution containing LiCl-KCl according to the mass ratio of the micro-nano particles to the LiCl-KCl of 1:1, and stirred for 6 hours until the micro-nano particles are uniformly mixed. Then, the stirring and heating temperature was raised to 75 ℃, and the mixture was stirred until most of the ethanol solution in the mixture had evaporated, and the substance was viscous. Finally, drying the viscous substance in a vacuum blowing drying oven at 120deg.C for 12 hr, and naturally cooling to obtain adhesive-free sea urchin-like V 2 O 5 LiCl-KCl electrode material.
Example 6
First, a certain amount of the molten salt LiF-LiCl-LiI was mixed into 30ml of ethanol solution, stirred constantly and the temperature was controlled at 50 ℃. Then sea urchin-like V with a particle size of about 10 μm 2 O 5 The micro-nano particles are slowly poured into a hot ethanol solution containing LiF-LiCl-LiI according to the mass ratio of LiCl-KCl of 3:2, and stirred for 4 hours until the mixture is uniform. Then, the stirring and heating temperature was raised to 75 ℃, and the mixture was stirred until most of the ethanol solution in the mixture had evaporated, and the substance was viscous. Finally, drying the viscous substance in a vacuum blowing drying oven at 180deg.C for 10 hr, and naturally cooling to obtain adhesive-free sea urchin-like V 2 O 5 LiF-LiCl-LiI electrode material.
Claims (5)
1. Adhesive-free V 2 O 5 The preparation method of the molten salt electrode material is characterized by comprising the following steps:
(1) Dissolving a certain amount of molten salt into a hot ethanol solution, and keeping the temperature of the hot ethanol solution at 50-70 ℃;
(2) Stirring sea urchin-like V 2 O 5 Slowly adding the micro-nano particles into a hot ethanol solution containing molten salt;
(3) Heating and stirring the mixed solution obtained in the step (2) in a water bath at 70-90 ℃ rapidly until most of ethanol is evaporated, wherein the mixed solution is sticky;
(4) Vacuum drying the viscous mixture obtained in step (3) at 120-180deg.C for 8-12 hr under vacuum condition until no ethanol solvent is present, and naturally cooling to obtain adhesive-free V 2 O 5 Molten salt electrode material;
the molten salt is one or more of LiF-LiCl-LiBr, liCl-KCl, liF-LiCl-LiI and LiCl-LiI;
said sea urchin shape V 2 O 5 The micro-nano particles are formed by V 2 O 5 Sea urchin balls with macroscopic and micrometer composition of nano particles, V 2 O 5 The nanoparticle has a size of 20-100nm, and is filled with molten salt and adhered to sea urchin-like V 2 O 5 The internal gaps and the surfaces of the micro-nano particles form a single adhesive-free type V 2 O 5 The size of the molten salt electrode material is 10-15 mu m;
the adhesive-free type V 2 O 5 The molten salt electrode material is in micro-nano granule shape and is prepared from molten salt and sea urchin-shaped V 2 O 5 Micro-nano particles are formed, and molten salt is uniformly embedded into sea urchin-shaped V 2 O 5 The sea urchin-like structure tightly binds the flowable molten salt in the micro-nano particle voids at high temperature.
2. Adhesive-free V according to claim 1 2 O 5 A method for producing a molten salt electrode material, characterized in that the sea urchin-like V 2 O 5 The preparation method of the micro-nano particles is as follows：
a. 3.6g oxalic acid and 0.4g cetyl trimethylammonium bromide were poured into 100mL distilled water and stirred continuously until completely dissolved;
b. pouring 2.34g of sodium metavanadate into the solution obtained in the step a, continuously stirring at normal temperature until the color of the solution is changed from yellow to orange, and then stirring for 2 hours;
c. transferring the solution obtained in the step b to a 200mL polytetrafluoroethylene reaction kettle, heating at 180 ℃ for 24 hours, and then cooling to normal temperature;
d. washing the hydro-thermal synthesis sample for three times by water, centrifuging and cleaning, and drying in vacuum at 90 ℃ for 12 hours;
e. heating the dried sample in a tube furnace at 3 deg.C/min to 500 deg.C in air environment, maintaining for 2 hr, and naturally cooling to room temperature to obtain sea urchin-like V 2 O 5 Micro-nano particles.
3. Adhesive-free V according to claim 1 2 O 5 A method for producing a molten salt electrode material, characterized by comprising the step (2) of providing a sea urchin-like shape V 2 O 5 The mass ratio of the micro-nano particles to the molten salt is (0.3-3.8): 0.2.
4. an adhesive-free V prepared by the process according to any one of claims 1 to 3 2 O 5 Molten salt electrode material.
5. The adhesive-free type V of claim 4 2 O 5 Use of a molten salt electrode material in the positive electrode of a thermal battery.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4119769A (en) * | 1976-04-09 | 1978-10-10 | Catalyst Research Corporation | Thermal battery having iron pyrite depolarizer |
| JP2004165131A (en) * | 2002-04-02 | 2004-06-10 | Nippon Shokubai Co Ltd | Ion conductor using de novo molten salt |
| CN104658771A (en) * | 2015-03-11 | 2015-05-27 | 重庆大学 | Method for preparing urchin-like vanadium base nanometer electrode material and application of the material |
| CN105789653A (en) * | 2016-04-13 | 2016-07-20 | 武汉理工大学 | Preparation method of thermal battery electrolyte containing hollow magnesia powder |
| CN110534697A (en) * | 2019-09-11 | 2019-12-03 | 中国工程物理研究院电子工程研究所 | A kind of single cell of thermo battery and preparation method thereof |
-
2021
- 2021-09-24 CN CN202111118278.5A patent/CN113851628B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4119769A (en) * | 1976-04-09 | 1978-10-10 | Catalyst Research Corporation | Thermal battery having iron pyrite depolarizer |
| JP2004165131A (en) * | 2002-04-02 | 2004-06-10 | Nippon Shokubai Co Ltd | Ion conductor using de novo molten salt |
| CN104658771A (en) * | 2015-03-11 | 2015-05-27 | 重庆大学 | Method for preparing urchin-like vanadium base nanometer electrode material and application of the material |
| CN105789653A (en) * | 2016-04-13 | 2016-07-20 | 武汉理工大学 | Preparation method of thermal battery electrolyte containing hollow magnesia powder |
| CN110534697A (en) * | 2019-09-11 | 2019-12-03 | 中国工程物理研究院电子工程研究所 | A kind of single cell of thermo battery and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Facile hydrothermal synthesis of double shelled Si@SnO2@C as advanced cathode for high-temperature lithium batteries;Yanyan Zhang，et al.;《Journal of Alloys and Compounds》;第1-11页 * |
| V2O5在NaCl-KCl-NaF熔盐体系中溶解度及溶解机理;武明雨等;《钢铁钒钛》;第24-29页 * |
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