CN108615884A - A kind of KFeF of hollow structure3Nano material and its preparation method and application - Google Patents
A kind of KFeF of hollow structure3Nano material and its preparation method and application Download PDFInfo
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- CN108615884A CN108615884A CN201810377906.3A CN201810377906A CN108615884A CN 108615884 A CN108615884 A CN 108615884A CN 201810377906 A CN201810377906 A CN 201810377906A CN 108615884 A CN108615884 A CN 108615884A
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- microemulsions
- kfef
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 24
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 70
- 239000002086 nanomaterial Substances 0.000 claims abstract description 54
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims abstract description 28
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 12
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012467 final product Substances 0.000 claims abstract description 11
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- -1 ethyl carbonate ester Chemical class 0.000 claims description 19
- 239000000839 emulsion Substances 0.000 claims description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011889 copper foil Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000006230 acetylene black Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910021135 KPF6 Inorganic materials 0.000 claims description 7
- 238000004080 punching Methods 0.000 claims description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- 239000012459 cleaning agent Substances 0.000 claims description 2
- 238000007581 slurry coating method Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01M4/582—Halogenides
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of KFeF of hollow structure3Nano material and its preparation method and application, preparation method include, by KF2H2O microemulsions are added dropwise to FeCl2·4H2It in O microemulsions, reacts 0.5 60min, adds reaction terminating agent and terminate reaction, cleaned after precipitation and separation to obtain the final product；KFeF3Nano material is the hollow structure of 10 50nm of grain size, and volume ratio shared by hollow structure inside is 25 80%；It has a extensive future in potassium ion button cell negative material.The present invention is only by by KF2H2O microemulsions are added dropwise to FeCl2·4H2In O microemulsions, while coordinating control KF2H2O and FeCl2·4H2The concentration and drop rate of O microemulsions realize the KFeF3 nano materials of controlledly synthesis difference size and the Bu Tong hollow structure of hollow size；Preparation condition is mild, simple for process controllable, efficient, is suitble to large-scale production, is widely used.
Description
Technical field
The present invention relates to technical field of nano material, and in particular to a kind of KFeF of hollow structure3Nano material and its system
Preparation Method and application.
Background technology
With the rapid development of social economy, energy crisis and environmental pollution have become two great societies that people face and ask
Topic, various novel energies have attracted the extensive attention of researcher.Secondary cell with high voltage and energy density due to forming
The object studied extensively for researcher, wherein lithium ion battery is to study at present most extensive and be commercially used the two of application
Primary cell.However, since the reserves in the earth's crust are few, the resource of lithium cannot be satisfied lithium ion battery future in worldwide
Be widely used；Researcher starts gradually to be transferred to research interest in the battery of alkali metal of rich reserves.
Kalium ion battery with the current potential close to lithium ion battery due to being concerned.For kalium ion battery cathode
For material, carbon material with rational specific capacity and reversible charge-discharge performance due to becoming preferred electrode material, but it has
Having the shortcomings that capacity is more relatively low than with cycle life, practical application is restricted greatly, therefore, research and development more suitably kalium ion battery
Negative material has important theory significance and practical value.
Perovskite-type fluorides KFeF3It is ground with its excellent ferromagnetism, electrical polarization characteristics and electroluminescence characters
Study carefully the common concern of personnel.KFeF3Due to being rich in K ions, it is made to have the potentiality as kalium ion battery negative material, and
Hollow KFeF with specific dimensions3Nano material can preferably store and discharge in kalium ion battery charge and discharge cycles potassium from
Son greatly improves its cycle performance and high rate performance；However, up to the present, the KFeF in relation to hollow structure3Nanometer material
There is not been reported for the preparation method of material.
In conclusion the KFeF of hollow structure how to be prepared by simple method3Nano material, and applied
It is the current key technical problem for being badly in need of solving in potassium ion button cell negative material.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of KFeF of hollow structure3Nano material and its preparation side
Method and application.
A kind of KFeF of hollow structure is provided according to an aspect of the present invention3The preparation method of nano material, including, it will
KF·2H2O microemulsions are added dropwise to FeCl2·4H2In O microemulsions, 0.5-60min is reacted, adds reaction terminating agent termination
It reacts, is cleaned after precipitation and separation to obtain the final product.
In above-mentioned reaction process, with KF2H2The dropwise addition dropwise of O microemulsions, KFeF3Nucleus is in microemulsion
Surface active groups gradually grow up, ultimately form the KFeF centered on active group3Reaction terminating is being added in nano material
Agent, which terminates, to be reacted and carries out in follow-up cleaning process, after the surface active groups in former microemulsion are cleaned out, is just formed hollow
The KFeF of structure3Nano material.
In the above-mentioned technical solutions, the FeCl2·4H2The molar concentration of O microemulsions is 0.01-0.1mol/L, described
KF·2H2O microemulsions and the FeCl2·4H2The molar concentration rate of O microemulsions is (3-5)：1, and corresponding to described in every 10mL
FeCl2·4H2O microemulsions, the KF2H2The drop rate of O microemulsions is 0.05-0.15mL/min.
Preferably, in the above-mentioned technical solutions, the FeCl2·4H2The molar concentration of O microemulsions is 0.05-0.08mol/
L, the KF2H2O microemulsions and the FeCl2·4H2The ratio of the molar concentration of O microemulsions is 4：1, and corresponding to per 10mL
The FeCl2·4H2O microemulsions, the KF2H2The drop rate of O microemulsions is 0.08-0.12mL/min.
In above-mentioned reaction process, the FeCl2·4H2O microemulsions and the KF2H2The concentration of O microemulsions and institute
State KF2H2KFeF of the rate of addition of O microemulsions to hollow structure3The forming process of nano material has a major impact, microemulsion
Excessive concentration or rate of addition is too fast can lead to K in reaction environment+、F-And Fe2+Concentration apparent surface's active group concentration
It is excessively high, to quickly form the micron order KFeF of solid construction3Material；And microemulsion concentration is too low or rate of addition excessively it is slow then without
Method generates the KFeF of hollow structure3Nano material.
Further, in the above-mentioned technical solutions, the FeCl2·4H2O microemulsions and the KF2H2O microemulsions by
FeCl2·4H2O and KF2H2O is added separately to be made in mixed emulsion；The mixed emulsion includes n-butanol, octane, goes
Ionized water and CTAB；
Preferably, in the above-mentioned technical solutions, in the mixed emulsion, the n-butanol, octane and deionized water
Volume ratio is (1.5-2.5)：(8-12)：The molar concentration of 1, the CTAB are 0.07-0.4mol/L.
In above-mentioned reaction process, the n-butanol provides microemulsion environment jointly with octane, and the deionized water is then
It is KFeF3Nucleus forming core site, is conducive to KFeF3Nucleus forming core is grown up；In addition, CTAB is selected to provide activity for surfactant
Group, effect are regulation and control KFeF3Appearance structure, ultimately form the KFeF of hollow structure3Nano material.
Further, in the above-mentioned technical solutions, the time of the reaction is 1-30min, preferably 8-15min.
Further, in the above-mentioned technical solutions, the reaction terminating agent is the mixed solution of chloroform and methanol.
Preferably, in the above-mentioned technical solutions, the volume ratio of the chloroform and methanol is (1-3)：1, more preferably
2：1.
And/or, it is preferable that in the above-mentioned technical solutions, the cleaning process uses methanol and deionized water conduct successively
Cleaning agent.
The KFeF for the hollow structure that above-mentioned preparation method obtains is provided according to a further aspect of the invention3Nano material.
Specifically, the KFeF3Nano material is the hollow structure of grain size 10-50nm, and hollow structure inside accounts for entirety
The percent by volume of structure is 25-80%.
Above-mentioned particle size range and the KFeF that the percent by volume of hollow structure is 25-80%3Nano material is due to specific surface
Product is high, big with electrolyte contacts area as cell negative electrode material, and reactivity is high, can bring high battery specific capacity.
Above-mentioned preparation method or above-mentioned KFeF are provided according to another aspect of the invention3Nano material is as potassium ion
The application of button cell negative material.
In addition, the present invention also provides a kind of potassium ion button cell negative material, specifically include pole piece, the pole piece by
Include the KFeF of above-mentioned hollow structure3The slurry of nano material is made.
Preferably, in the slurry, the KFeF3The mass ratio of nano material, PVDF and acetylene black is (6-8)：
(1.8-2.4)：1.
It is further preferred that the preparation method of the pole piece is as follows：Using DMF as solvent, by KFeF3Nano material, PVDF
Slurry is made after being dissolved in the solvent with acetylene black, the slurry coating is placed on copper foil in 80 DEG C of vacuum drying chamber
Dry 10-14h, after punching to obtain the final product.
In addition, invention further provides a kind of potassium ion button cell, including the cathode made of above-mentioned negative material.
Preferably, the electrolyte of the potassium ion button cell is the ethyl carbonate ester solution of 1.0mol/L KPF6, diaphragm
For celgard2400 films.
Advantages of the present invention：
(1) present invention is only by by KF2H2O microemulsions are added dropwise to FeCl2·4H2In O microemulsions, coordinate simultaneously
Control KF2H2O microemulsions and FeCl2·4H2The concentration of O microemulsions and its drop rate, can be prepared different sizes
With the KFeF of Bu Tong hollow size3Nano material, to realize the KFeF of hollow structure3The controlledly synthesis of nano material；
(2) KFeF for the hollow structure being prepared using method provided by the present invention3Nano material size is small, grain size
For 10-50nm, it is 20-80%, the KFeF that hollow structure, which accounts for integrally-built volume ratio,3The specific surface area of nano-grain
Greatly, as cell negative electrode material, big with the contact area of electrolyte during the reaction, reactivity is high, to effectively carry
The high specific capacity of battery；
(3) KFeF for preparing hollow structure that the present invention is developed3The method mild condition of nano material, it is simple for process can
Control, product chemistry structure and performance are stablized, and used raw material is easy to get and cheap, and production equipment is simple, and production efficiency is high,
It is suitble to scale industrial production, and the KFeF of obtained hollow structure3The electric property of nanomaterial product is excellent, before
Scape is wide, and theoretical and practical significance is great.
Description of the drawings
Fig. 1 is the KFeF of hollow structure prepared in the embodiment of the present invention 13The X-ray diffractogram of nano material；
Fig. 2 is the KFeF of hollow structure prepared in the embodiment of the present invention 13The transmission electron microscope and high-resolution of nano material
Transmission electron microscope picture；
Fig. 3 is the KFeF of hollow structure prepared in the embodiment of the present invention 13Nano material is as kalium ion battery cathode
Charge-discharge performance result figure when material.
Specific implementation mode
With reference to the accompanying drawings and examples, the specific implementation mode of the present invention is described in further detail.Implement below
Example is not limited to protection scope of the present invention for illustrating the present invention, and protection scope of the present invention is with claims
It is accurate.
In the examples below, X-ray diffractogram is obtained using X-ray diffractometer (Bruker D8 Focus)；Transmission electricity
Mirror and high-resolution-ration transmission electric-lens photo are obtained using Hitachi S-4800 transmission electron microscopes；Kalium ion battery negative material
Charge-discharge performance test test to obtain using Wuhan indigo plant electric tester.
Embodiment 1
An embodiment of the present invention provides a kind of KFeF of hollow structure3The preparation method of nano material, is as follows：
(1) 1.5ml n-butanols, 7.5ml octanes, 0.75ml deionized waters and 0.1mol CTAB are measured respectively at twice, is mixed
Conjunction obtains two parts of mixed emulsions；
(2) 0.1g FeCl are weighed2·4H2O and 0.19g KF2H2O powder is separately added into two parts of step (1) preparation
In mixed emulsion, it is stirred by ultrasonic uniformly to get FeCl2·4H2O microemulsions and KF2H2O microemulsions；
(3) by KF2H2O microemulsions are added dropwise to FeCl with the drop rate of 0.1mL/min2·4H2In O microemulsions,
After reacting 30min, it is 1 that 30ml volume ratios, which are added,:1 chloroform and the mixed solution of methanol terminate reaction, and separation takes brown
Color precipitates, and uses volume ratio for 5:1 methanol and deionized water solution cleans the KFeF to get final product hollow structure3
Nano material.
Kalium ion battery KFeF prepared by the present invention3The application of nano particle negative material, KFeF3Nano particle cathode
Material is applied to button cell, and cathode use DMF for solvent, and the formula of pole piece is KFeF according to mass ratio3Nano particle：
PVDF：Acetylene black is 7：2：1 ratio is modulated into slurry, and then slurry is coated uniformly on copper foil, and copper foil is put into vacuum
In drying box after 80 DEG C of drying 12h, experimental cell pole piece is obtained after punching, using metallic potassium as to electrode, electrolyte
For the ethyl carbonate ester of 1.0M KPF6, (volume ratio of EC and dimethyl carbonate is 1:1) solution, diaphragm are
Celgard2400 films, are assembled into button cell in the glove box full of argon gas atmosphere.
Charge and discharge cycles test is carried out to the button cell：Charge and discharge blanking voltage is 0.01-2.6V, and charging or discharging current is
500mA/g。
Embodiment 2
An embodiment of the present invention provides a kind of KFeF of hollow structure3The preparation method of nano material, is as follows：
(1) 1.5ml n-butanols, 7.5ml octanes, 0.75ml deionized waters and 0.1mol CTAB are measured respectively at twice, is mixed
Conjunction obtains two parts of mixed emulsions；
(2) 0.2g FeCl are weighed2·4H2O and 0.19g KF2H2O powder is separately added into two parts of step (1) preparation
In mixed emulsion, it is stirred by ultrasonic uniformly to get FeCl2·4H2O microemulsions and KF2H2O microemulsions；
(3) by KF2H2O microemulsions are added dropwise to FeCl with the drop rate of 0.1mL/min2·4H2In O microemulsions,
After reacting 30min, it is 1 that 30ml volume ratios, which are added,:1 chloroform and the mixed solution of methanol terminate reaction, and separation takes brown
Color precipitates, and uses volume ratio for 5:1 methanol and deionized water solution cleans the KFeF to get final product hollow structure3
Nano material.
Kalium ion battery KFeF prepared by the present invention3The application of nano particle negative material, KFeF3Nano particle cathode
Material is applied to button cell, and cathode use DMF for solvent, and the formula of pole piece is KFeF according to mass ratio3Nano particle：
PVDF：Acetylene black is 7：2：1 ratio is modulated into slurry, and then slurry is coated uniformly on copper foil, and copper foil is put into vacuum
In drying box after 80 DEG C of drying 12h, experimental cell pole piece is obtained after punching, using metallic potassium as to electrode, electrolyte
For the ethyl carbonate ester of 1.0M KPF6, (volume ratio of EC and dimethyl carbonate is 1:1) solution, diaphragm are
Celgard2400 films, are assembled into button cell in the glove box full of argon gas atmosphere.
Charge and discharge cycles test is carried out to the button cell：Charge and discharge blanking voltage is 0.01-2.6V, and charging or discharging current is
500mA/g。
Embodiment 3
An embodiment of the present invention provides a kind of KFeF of hollow structure3The preparation method of nano material, is as follows：
(1) 1.5ml n-butanols, 7.5ml octanes, 0.75ml deionized waters and 0.1mol CTAB are measured respectively at twice, is mixed
Conjunction obtains two parts of mixed emulsions；
(2) 0.2g FeCl are weighed2·4H2O and 0.19g KF2H2O powder is separately added into two parts of step (1) preparation
In mixed emulsion, it is stirred by ultrasonic uniformly to get FeCl2·4H2O microemulsions and KF2H2O microemulsions；
(3) by KF2H2O microemulsions are added dropwise to FeCl with the drop rate of 0.1mL/min2·4H2In O microemulsions,
After reacting 30min, it is 1 that 30ml volume ratios, which are added,:1 chloroform and the mixed solution of methanol terminate reaction, and separation takes brown
Color precipitates, and uses volume ratio for 5:1 methanol and deionized water solution cleans the KFeF to get final product hollow structure3
Nano material.
Kalium ion battery KFeF prepared by the present invention3The application of nano particle negative material, KFeF3Nano particle cathode
Material is applied to button cell, and cathode use DMF for solvent, and the formula of pole piece is KFeF according to mass ratio3Nano particle：
PVDF：Acetylene black is 7：2：1 ratio is modulated into slurry, and then slurry is coated uniformly on copper foil, and copper foil is put into vacuum
In drying box after 80 DEG C of drying 12h, experimental cell pole piece is obtained after punching, using metallic potassium as to electrode, electrolyte
For the ethyl carbonate ester of 1.0M KPF6, (volume ratio of EC and dimethyl carbonate is 1:1) solution, diaphragm are
Celgard2400 films, are assembled into button cell in the glove box full of argon gas atmosphere.
Charge and discharge cycles test is carried out to the button cell：Charge and discharge blanking voltage is 0.01-2.6V, and charging or discharging current is
500mA/g。
Embodiment 4
An embodiment of the present invention provides a kind of KFeF of hollow structure3The preparation method of nano material, is as follows：
(1) 1.5ml n-butanols, 7.5ml octanes, 0.75ml deionized waters and 0.1mol CTAB are measured respectively at twice, is mixed
Conjunction obtains two parts of mixed emulsions；
(2) 0.4g FeCl are weighed2·4H2O and 0.19g KF2H2O powder is separately added into two parts of step (1) preparation
In mixed emulsion, it is stirred by ultrasonic uniformly to get FeCl2·4H2O microemulsions and KF2H2O microemulsions；
(3) by KF2H2O microemulsions are added dropwise to FeCl with the drop rate of 0.1mL/min2·4H2In O microemulsions,
After reacting 30min, it is 1 that 30ml volume ratios, which are added,:1 chloroform and the mixed solution of methanol terminate reaction, and separation takes brown
Color precipitates, and uses volume ratio for 5:1 methanol and deionized water solution cleans the KFeF to get final product hollow structure3
Nano material.
Kalium ion battery KFeF prepared by the present invention3The application of nano particle negative material, KFeF3Nano particle cathode
Material is applied to button cell, and cathode use DMF for solvent, and the formula of pole piece is KFeF according to mass ratio3Nano particle：
PVDF：Acetylene black is 7：2：1 ratio is modulated into slurry, and then slurry is coated uniformly on copper foil, and copper foil is put into vacuum
In drying box after 80 DEG C of drying 12h, experimental cell pole piece is obtained after punching, using metallic potassium as to electrode, electrolyte
For the ethyl carbonate ester of 1.0M KPF6, (volume ratio of EC and dimethyl carbonate is 1:1) solution, diaphragm are
Celgard2400 films, are assembled into button cell in the glove box full of argon gas atmosphere.
Charge and discharge cycles test is carried out to the button cell：Charge and discharge blanking voltage is 0.01-2.6V, and charging or discharging current is
500mA/g。
Embodiment 5
An embodiment of the present invention provides a kind of KFeF of hollow structure3The preparation method of nano material, is as follows：
(1) 1.5ml n-butanols, 7.5ml octanes, 0.75ml deionized waters and 0.1mol CTAB are measured respectively at twice, is mixed
Conjunction obtains two parts of mixed emulsions；
(2) 0.2g FeCl are weighed2·4H2O and 0.38g KF2H2O powder is separately added into two parts of step (1) preparation
In mixed emulsion, it is stirred by ultrasonic uniformly to get FeCl2·4H2O microemulsions and KF2H2O microemulsions；
(3) by KF2H2O microemulsions are added dropwise to FeCl with the drop rate of 0.1mL/min2·4H2In O microemulsions,
After reacting 30min, it is 1 that 30ml volume ratios, which are added,:1 chloroform and the mixed solution of methanol terminate reaction, and separation takes brown
Color precipitates, and uses volume ratio for 5:1 methanol and deionized water solution cleans the KFeF to get final product hollow structure3
Nano material.
Kalium ion battery KFeF prepared by the present invention3The application of nano particle negative material, KFeF3Nano particle cathode
Material is applied to button cell, and cathode use DMF for solvent, and the formula of pole piece is KFeF according to mass ratio3Nano particle：
PVDF：Acetylene black is 7：2：1 ratio is modulated into slurry, and then slurry is coated uniformly on copper foil, and copper foil is put into vacuum
In drying box after 80 DEG C of drying 12h, experimental cell pole piece is obtained after punching, using metallic potassium as to electrode, electrolyte
For the ethyl carbonate ester of 1.0M KPF6, (volume ratio of EC and dimethyl carbonate is 1:1) solution, diaphragm are
Celgard2400 films, are assembled into button cell in the glove box full of argon gas atmosphere.
Charge and discharge cycles test is carried out to the button cell：Charge and discharge blanking voltage is 0.01-2.6V, and charging or discharging current is
500mA/g。
Comparative example
Comparative example of the present invention provides a kind of KFeF3The preparation method of nano material, is as follows：
(1) 1.5ml n-butanols, 7.5ml octanes, 0.75ml deionized waters and 0.1mol CTAB are measured respectively at twice, is mixed
Conjunction obtains two parts of mixed emulsions；
(2) 2.5g FeCl are weighed2·4H2O and 0.76g KF2H2O powder is separately added into two parts of step (1) preparation
In mixed emulsion, it is stirred by ultrasonic uniformly to get FeCl2·4H2O microemulsions and KF2H2O microemulsions；
(3) by KF2H2O microemulsions are added dropwise to FeCl with the drop rate of 0.4mL/min2·4H2In O microemulsions,
After reacting 30min, it is 1 that 30ml volume ratios, which are added,:1 chloroform and the mixed solution of methanol terminate reaction, and separation takes brown
Color precipitates, and uses volume ratio for 5:1 methanol and deionized water solution cleans to get final product KFeF3Nano material.
It is as shown in Figure 1 the KFeF of hollow structure prepared in the embodiment of the present invention 13The XRD spectrum of nano material, will
Fig. 1 is compared with standard card (PDF#20-0895) it is found that obtained product is KFeF3Object phase.
It is illustrated in figure 2 the KFeF of hollow structure prepared in the embodiment of the present invention 13The TEM of nano material schemes, from figure
As can be seen that KFeF in 23The grain size of nano material is in hollow form structure between 10-50nm；In HRTRM figures,
By measuring the interplanar distance of product, it is found that surveyed interplanar distance is 0.41nm, in corresponding standard card (PDF#20-0895)
(100) crystal face.
It is illustrated in figure 3 the KFeF of hollow structure prepared in the embodiment of the present invention 13Nano material is as potassium ion knob
The charge-discharge test curve of battery cathode is detained, in first lap discharge process, battery specific capacity has reached 344mAh/g, passes through
Specific capacity after 100 circle charge and discharge is still up to 172mAh/g.
Meanwhile by preparation-obtained KFeF in comparative example3Nano material does TEM tests, the results showed that, it is prepared
KFeF3Nano material is solid construction, and granular size, between 150nm-0.2 μm, particle size distribution is big and without apparent rule
Rule.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that：It still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features；
And these modifications or replacements, various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of KFeF of hollow structure3The preparation method of nano material, which is characterized in that including by KF2H2O microemulsions by
It is added dropwise to FeCl2·4H2In O microemulsions, 0.5-60min is reacted, reaction terminating agent is added and terminates and react, after precipitation and separation
It cleans to obtain the final product.
2. preparation method according to claim 1, which is characterized in that the FeCl2·4H2The molar concentration of O microemulsions is
0.01-0.1mol/L, the KF2H2O microemulsions and the FeCl2·4H2The molar concentration rate of O microemulsions is (3-5)：1,
And corresponding to FeCl described in every 10mL2·4H2O microemulsions, the KF2H2The drop rate of O microemulsions is 0.05-0.15mL/
min；
Preferably, the FeCl2·4H2The molar concentration of O microemulsions is 0.05-0.08mol/L, the KF2H2O microemulsions
With the FeCl2·4H2The ratio of the molar concentration of O microemulsions is 4：1, and corresponding to FeCl described in every 10mL2·4H2O micro emulsions
Liquid, the KF2H2The drop rate of O microemulsions is 0.08-0.12mL/min.
3. preparation method according to claim 1 or 2, which is characterized in that the FeCl2·4H2O microemulsions and described
KF·2H2O microemulsions are by FeCl2·4H2O and KF2H2O is added separately to be made in mixed emulsion；It is wrapped in the mixed emulsion
Include n-butanol, octane, deionized water and CTAB；
Preferably, in the mixed emulsion, the volume ratio of the n-butanol, octane and deionized water is (1.5-2.5)：(8-
12)：The molar concentration of 1, the CTAB are 0.07-0.4mol/L.
4. preparation method according to claim 1 or 2, which is characterized in that the time of the reaction is 1-30min, preferably
For 8-15min.
5. preparation method according to claim 1 or 2, which is characterized in that the reaction terminating agent is chloroform and first
The mixed solution of alcohol；
Preferably, the volume ratio of the chloroform and methanol is (1-3)：1, more preferably 2：1；
And/or the cleaning process uses methanol and deionized water as cleaning agent successively.
6. according to the KFeF for the hollow structure that claim 1-5 any one of them preparation methods obtain3Nano material.
7. KFeF according to claim 63Nano material, which is characterized in that the KFeF3Nano material is grain size 10-
The hollow structure of 50nm, and it is 25-80% that hollow structure inside, which accounts for integrally-built percent by volume,.
8. according to claim 1-5 any one of them preparation method or claim 6-7 any one of them KFeF3Nanometer material
Expect the application as potassium ion button cell negative material.
9. a kind of potassium ion button cell negative material, which is characterized in that including pole piece, the pole piece is by including claim 7
Or 8 KFeF3The slurry of nano material is made；
Preferably, in the slurry, the KFeF3The mass ratio of nano material, PVDF and acetylene black is (6-8)：(1.8-
2.4)：1；
It is further preferred that the preparation method of the pole piece is as follows：Using DMF as solvent, by KFeF3Nano material, PVDF and acetylene
It is black be dissolved in the solvent after slurry is made, the slurry coating is placed on copper foil in 80 DEG C of vacuum drying chamber dry
10-14h, after punching to obtain the final product.
10. a kind of potassium ion button cell, it is characterised in that：It include the cathode made of the negative material described in claim 9；
Preferably, the electrolyte of the potassium ion button cell is the ethyl carbonate ester solution of 1.0mol/L KPF6, and diaphragm is
Celgard2400 films.
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| CN115954482A (en) * | 2023-03-15 | 2023-04-11 | 江苏正力新能电池技术有限公司 | Layered oxide composite material, preparation method thereof, positive plate and sodium ion battery |
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| CN101085465A (en) * | 2007-06-15 | 2007-12-12 | 中国科学技术大学 | Method for preparing titanium dioxide hollow sphere containing gold nano particles |
| EP2634783A1 (en) * | 2010-10-27 | 2013-09-04 | Ocean's King Lighting Science&Technology Co., Ltd. | Composite electrode material, manufacturing method and application thereof |
| CN103560231A (en) * | 2013-09-27 | 2014-02-05 | 江苏华东锂电技术研究院有限公司 | Lithium ion battery anode composite material and its preparation method |
| CN106853997A (en) * | 2016-12-14 | 2017-06-16 | 北京理工大学 | A kind of positive electrode and preparation method thereof and positive pole coating material and lithium ion battery |
| CN107487787A (en) * | 2017-10-12 | 2017-12-19 | 北京科技大学 | A kind of hollow KMnF3The preparation method of nanometer square particle |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085465A (en) * | 2007-06-15 | 2007-12-12 | 中国科学技术大学 | Method for preparing titanium dioxide hollow sphere containing gold nano particles |
| EP2634783A1 (en) * | 2010-10-27 | 2013-09-04 | Ocean's King Lighting Science&Technology Co., Ltd. | Composite electrode material, manufacturing method and application thereof |
| CN103560231A (en) * | 2013-09-27 | 2014-02-05 | 江苏华东锂电技术研究院有限公司 | Lithium ion battery anode composite material and its preparation method |
| CN106853997A (en) * | 2016-12-14 | 2017-06-16 | 北京理工大学 | A kind of positive electrode and preparation method thereof and positive pole coating material and lithium ion battery |
| CN107487787A (en) * | 2017-10-12 | 2017-12-19 | 北京科技大学 | A kind of hollow KMnF3The preparation method of nanometer square particle |
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| CN115954482A (en) * | 2023-03-15 | 2023-04-11 | 江苏正力新能电池技术有限公司 | Layered oxide composite material, preparation method thereof, positive plate and sodium ion battery |
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