CN110137480A - Kalium ion battery positive electrode rubidium doping phosphoric acid vanadium potassium/carbon composite preparation method - Google Patents
Kalium ion battery positive electrode rubidium doping phosphoric acid vanadium potassium/carbon composite preparation method Download PDFInfo
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- CN110137480A CN110137480A CN201910494000.4A CN201910494000A CN110137480A CN 110137480 A CN110137480 A CN 110137480A CN 201910494000 A CN201910494000 A CN 201910494000A CN 110137480 A CN110137480 A CN 110137480A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/58—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses high-performance rubidium doping phosphoric acid vanadium potassium/carbon composite preparation methods, form homogeneous solution by reaction raw materials and chelating agent, using vanadium phosphate potassium/carbon composite of the rubidium doping of collosol and gel combination high-temperature calcination preparation high activity.The carbon of chelating agent in-situ preparation highly electron conductive under high temperature inert atmospheric condition in the present invention, carbon can not only be used as reducing agent in high-temperature calcination, but also can inhibit growing up and reuniting for product grain.Potassium potential mixes rubidium and provides bigger channel for the migration of potassium ion, while carbon coating improves the electronic conductivity of material, so that vanadium phosphate potassium/carbon composite of rubidium doping has excellent chemical property.
Description
Technical field
The invention belongs to technical field of energy material, in particular to a kind of high-performance rubidium doping phosphoric acid vanadium potassium/carbon composite wood
The preparation method of material.
Background technique
Develop energy conservation technology and new energy power generation technology (solar power generation, wind power generation, geother-mal power generation and ocean
Can power generation etc.), it has also become countries in the world successfully manage the fossil fuels such as coal, petroleum largely consume and bring environmental pollution and
The high effective way of energy crisis.But since new energy power generation technology is larger in the presence of intermittent, randomness and energy supply fluctuation
The shortcomings that, lead to the development of new energy power generation technology and efficiently utilizes the energy storage technology for being limited by existing backwardness, therefore, advanced storage
The development of energy technology will promote the rapid development of new energy power generation technology, be conducive to the sustainable development of society.It is stored up with physics
Can technology compare, electrochemical energy storage technology has many advantages, such as cheap, high conversion efficiency, is not restricted by place, becomes advanced
The development priority of energy storage technology.In various electrochemical energy storage technologies, lithium ion battery because its energy density with higher, compared with
Long service life, it is light-weight and adaptable the advantages that, the biggish market share is occupied in electrochemical energy storage technology.So
And with scale energy storage and the extensive use of electric car, that there are lithium resources is deficient, expensive because of it for lithium ion battery,
The disadvantages such as power density is low, have been difficult to meet the needs of large-scale application, therefore, the electrochemical energy storage technology of Development of Novel has become
For the emphasis of electrochmical power source research.Because of rich reserves (about more than 1000 times of lithium), the widely distributed and valence of sodium, potassium in the earth's crust
Lattice are cheap, sodium-ion battery and kalium ion battery with reaction mechanism similar to lithium ion battery, become electrochmical power source research
New focus.
Compared with sodium-ion battery, the kalium ion battery advantage incomparable with some sodium-ion batteries.With Li+And Na+
It compares, due to K+Lewis acidity is weaker, leads to K+Solvated ion radius be less than Li+And Na+Solvated ion radius,
Solvation K+Ionic conductivity and transfer number be higher than Li+And Na+, and solvation K+Energy needed for desolvation is lower, because
And K+With the dynamic performance quickly spread between electrolyte/electrode interface, these advantages make times of kalium ion battery
Rate performance is theoretically better than sodium-ion battery and lithium ion battery.However, with the lithium ion battery of technology relative maturity and
At present study more sodium-ion battery is compared, at present kalium ion battery technology very fall behind, kalium ion battery is ground
Study carefully seldom, the research of kalium ion battery is still at an early stage.It finds and is suitble to large radius K+Insertion/deintercalation electrode material becomes
The key of kalium ion battery hair development at present, developing kalium ion battery positive electrode and negative electrode material becomes current kalium ion battery
Research emphasis.
Potassium fast-ionic conductor vanadium phosphate potassium (K3V2(PO4)3), have stable structure, operating voltage be high, diffusion admittance greatly with
And the advantages that having a safety feature, it is a kind of great kalium ion battery positive electrode for having application prospect.But due to its electronic conductance
Rate is relatively low and thus causes the disadvantages of activation polarization is bigger, cycle performance is poor and actual capacity is relatively low, causes
Its actual chemical property is poor, it is difficult to practical application.
The present invention is directed to the shortcomings that vanadium phosphate potassium and current present Research, improves electronic conductivity and potassium using carbon coating
Position doping large radius ion improves the strategy that ion diffusion rates combine, by the way that low energy consumption and easy-operating sol-gel method
Prepare potassium potential rubidium doping phosphoric acid vanadium potassium/carbon composite (K3-xRbxV2(PO4)3/ C), significantly improve the electrochemistry of vanadium phosphate potassium
Can, scientific research and its industrialization to vanadium phosphate potassium all have more important meaning.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of high-performance rubidium doping phosphoric acid vanadium potassium/carbon composite, should
Method and process is simple, low energy consumption, and the kalium ion battery positive electrode of preparation has capacity height, has extended cycle life, high-rate performance
The excellent and high advantage of energy density.
In order to achieve the above objectives, the technical solution adopted by the present invention are as follows:
A kind of kalium ion battery positive electrode rubidium doping phosphoric acid vanadium potassium/carbon composite, the material have three-dimensional network frame
Frame structure, can allow for K+Quickly through and can be in K+Stable structure is maintained in deintercalation and telescopiny.Kalium ion battery anode
Rubidium doping phosphoric acid vanadium potassium in material rubidium doping phosphoric acid vanadium potassium/carbon is with K3-xRbxV2(PO4)3It indicates, the preparation of the positive electrode
Method, comprising the following steps:
(1) by vanadium source compound, P source compound, potassium resource compound, rubidium source compound, chelating agent V:P:K in molar ratio:
Rb:C=2:3:(3-x): x:6 weighs (wherein 0≤x≤0.3), and is dissolved in a certain amount of distilled water, heats while stirring, instead
Moisture should be evaporated completely after a certain period of time, obtain blue or light green color xerogel；
(2) xerogel in (1) is dried, and the gel after drying is placed under inert atmosphere conditions, and with 2 DEG C/min
The heating rate of~10 DEG C/min is heated to 700 DEG C~1000 DEG C, constant temperature 4h~12h, cools to room temperature with the furnace to get black is arrived
Kalium ion battery positive electrode K3-xRbxV2(PO4)3/ C composite.
The vanadium source compound is one of vanadic anhydride, ammonium metavanadate, vanadium oxytrichloride, vanadic sulfate or a variety of；
Phosphorus source compound be one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphorus pentoxide, potassium dihydrogen phosphate or
It is a variety of；The potassium resource compound is potassium hydroxide, potassium carbonate, saleratus, potassium nitrate, potassium acetate, one in potassium dihydrogen phosphate
Kind is a variety of；The rubidium source compound is one of rubidium carbonate, rubidium nitrate, rubidium acetate, rubidium sulfate, rubidium chloride, rubidium perchlorate
Or it is a variety of；The chelating agent is one of citric acid, oxalic acid, tartaric acid, ethylenediamine tetra-acetic acid or a variety of；The inert atmosphere
For one or both of nitrogen, argon gas.The kalium ion battery that the kalium ion battery positive electrode is assembled into is by potassium ion electricity
Pond positive plate, negative electrode tab, diaphragm, electrolyte assemble, wherein positive plate by kalium ion battery positive electrode and conductive agent and
It is made after binder mixing, negative electrode tab is metallic potassium, and diaphragm is fibreglass diaphragm, electrolyte KPF6Polycarbonate it is molten
Liquid.
The present invention is by water-soluble substances such as vanadium source compound, P source compound, potassium resource compound, rubidium source compounds and chelates
Agent effect has powerful chelation using chelating agent, and reactant is made to reach uniform mixed on molecular level in aqueous solution
It closes, be conducive to reaction in lower temperature and completed in the short period, and obtain the lesser product of particle size.Existed using chelating agent
The process of carbonization under high temperature forms the carbon coating of highly electron conductive in reaction-ure surface, can both play pyroreaction generation
The effect of doping phosphoric acid vanadium potassium can also be played and doping phosphoric acid vanadium potassium product grain is inhibited to reunite and grow up, help to obtain ruler
Very little lesser carbon coating doping phosphoric acid vanadium potassium.The carbon coating layer of residual in the product has highly electron conductive, is conducive to improve
The electronic conductivity of material, and K can be expanded by introducing large radius Doped ions in potassium potential+Diffusion admittance, be conducive to potassium ion
Quick deintercalation and insertion, to obtain rubidium doping phosphoric acid vanadium potassium/carbon composite of electrochemical performance.
Detailed description of the invention
Fig. 1 is vanadium phosphate potassium/carbon x-ray diffraction pattern prepared by case study on implementation 1 of the present invention.
Fig. 2 be vanadium phosphate potassium/carbon for preparing of case study on implementation 1 of the present invention as kalium ion battery positive electrode 2.5~
In the voltage range of 4.6V and current density is 20mAg-1Under the conditions of first charge-discharge curve.
Fig. 3 be vanadium phosphate potassium/carbon for preparing of case study on implementation 1 of the present invention as kalium ion battery positive electrode 2.5~
In the voltage range of 4.6V and current density is 20mAg-1Under the conditions of cycle performance figure.
Fig. 4 is rubidium doping phosphoric acid vanadium potassium/carbon x-ray diffraction pattern prepared by case study on implementation 2 of the present invention.
Fig. 5 is rubidium doping phosphoric acid vanadium potassium/carbon scanning electron microscope (SEM) photograph prepared by embodiment of the present invention example 2.
Fig. 6 is that rubidium doping phosphoric acid vanadium potassium/carbon prepared by case study on implementation 2 of the present invention exists as kalium ion battery positive electrode
In the voltage range of 2.5~4.6V and current density is 20mAg-1Under the conditions of first charge-discharge curve.
Fig. 7 is that rubidium doping phosphoric acid vanadium potassium/carbon prepared by case study on implementation 2 of the present invention exists as kalium ion battery positive electrode
In the voltage range of 2.5~4.6V and current density is 20mAg-1Under the conditions of cycle performance figure.
The concrete mode of case study on implementation
Case study on implementation of the present invention is described further below.
Case study on implementation 1:
Weigh 0.03mol ammonium metavanadate, 0.045mol ammonium dihydrogen phosphate, 0.045mol potassium acetate, 0.09mol citric acid etc.
Reactant, and its whole is added in the beaker of 100mL, it is added in 80mL distilled water, it is strong to stir, it is lauched in 80 DEG C of conditions
Bath is evaporated.Colloidal sol after being evaporated is placed in the convection oven that temperature is 120 DEG C, dry 8h.By the mixture transfer after drying
Into tube furnace, under argon atmosphere protection, 800 DEG C, constant temperature 10h are heated to the heating rate of 10 DEG C/min, furnace cooling
To room temperature to get arrive kalium ion battery positive electrode K3V2(PO4)3/ C composite.Fig. 1 is the x-ray diffraction pattern of the material.
The kalium ion battery positive electrode K that will be prepared3V2(PO4)3/ C composite, acetylene black and PVDF press quality
It is more uniform than for the ratio ground and mixed of 8:1:1, suitable NMP is added dropwise, electrode slurry is made, then again applies slurry on aluminium foil
Mill uniformly, is placed in 120 DEG C of vacuum ovens and sufficiently dries, and being cut into diameter is the paillon of 15mm as Electrode, with to roller
Machine compacting.Using the positive plate being prepared as positive electrode, using metallic potassium piece as cathode, with 0.8molL-1KPF6Poly- carbon
Acid esters solution is as electrolyte, and diaphragm is Whatman fibreglass diaphragm, in the glove box (water full of dry high-purity argon gas
Point and oxygen content be both less than 0.1ppm) in dress up CR2016 type button cell.Button cell is placed on battery test system,
It is tested in room temperature charge-discharge performance.When current density is 20mA/g and charging/discharging voltage range is 2.5~4.6V (vs.K+/K)
Under conditions of, reversible discharge capacity is 41.7mAhg for the first time-1, after recycling 100 times, capacity remains 23.4mAhg-1。
Fig. 2 and Fig. 3 is respectively in the first charge-discharge curve and cycle performance figure of the material.
Case study on implementation 2:
Weigh 0.015mol vanadic anhydride, 0.045mol ammonium dihydrogen phosphate, 0.04425mol potassium acetate, 0.00075mol
The reactants such as rubidium acetate and 0.09mol citric acid, and its whole is added in the beaker of 100mL, 80mL distilled water is added, by force
Strong stirring, water bath method under the conditions of 80 DEG C.Colloidal sol after being evaporated is placed in the convection oven that temperature is 120 DEG C, it is dry
10h.Mixture after drying is transferred in tube furnace, under argon atmosphere protection, is heated to the heating rate of 2 DEG C/min
700 DEG C, constant temperature 6h, room temperature is cooled to the furnace to get kalium ion battery positive electrode K is arrived2.95Rb0.05V2(PO4)3/ C composite wood
Material.Fig. 4 is the x-ray diffraction pattern of the material, and Fig. 5 is the scanning electron microscope (SEM) photograph of the material.
The potassium ion positive electrode K that will be prepared2.95Rb0.05V2(PO4)3/ C composite, acetylene black and PVDF press matter
Amount is more uniform than for the ratio ground and mixed of 8:1:1, suitable NMP is added dropwise, electrode slurry is made, then again by slurry on aluminium foil
Apply mill uniformly, be placed in 120 DEG C of vacuum ovens sufficiently dry, be cut into paillon that diameter is 15mm as Electrode, with pair
The compacting of roller machine.Using the positive plate being prepared as positive electrode, using metallic potassium piece as cathode, with 0.8molL-1KPF6It is poly-
Carbonate solution is as electrolyte, and diaphragm is Whatman fibreglass diaphragm, in the glove box full of dry high-purity argon gas
CR2016 type button cell is dressed up in (moisture and oxygen content are both less than 0.1ppm).Button cell is placed in battery test system
On, it is tested in room temperature charge-discharge performance, when current density is 20mA/g and charging/discharging voltage range is 2.5~4.6V (vs.K+/ K) under conditions of, the second circle reversible discharge capacity is 51.46mAhg-1, after recycling 100 times, capacity is remained
31.76mAh·g-1.Fig. 6 and Fig. 7 is respectively the first charge-discharge curve and cycle performance curve of the material.
Case study on implementation 3:
Weigh 0.03mol vanadic sulfate, 0.045mol ammonium dihydrogen phosphate, 0.0435mol potassium acetate, 0.0015mol nitric acid
The reactants such as rubidium and 0.09mol citric acid, and its whole is added in the beaker of 100mL, 75mL distilled water is added, stirs strongly
It mixes, water bath method under the conditions of 60 DEG C.Colloidal sol after being evaporated is placed in the convection oven that temperature is 120 DEG C, dry 12h.It will
Mixture after drying is transferred in tube furnace, under argon atmosphere protection, is heated to 750 DEG C with the heating rate of 3 DEG C/min,
Constant temperature 9h cools to room temperature with the furnace to get kalium ion battery positive electrode K is arrived2.9Rb0.1V2(PO4)3/ C composite.
The kalium ion battery positive electrode K that will be prepared2.9Rb0.1V2(PO4)3/ C composite, acetylene black and PVDF are pressed
Mass ratio is that the ratio ground and mixed of 8:1:1 is uniform, suitable NMP is added dropwise, electrode slurry is made, then again by slurry in aluminium foil
Upper painting mill uniformly, is placed in 120 DEG C of vacuum ovens and sufficiently dries, and being cut into diameter is the paillon of 15mm as Electrode, uses
Twin rollers compacting.Using the positive plate being prepared as positive electrode, using metallic potassium piece as cathode, with 0.8molL-1KPF6's
Polycarbonate solution is as electrolyte, and diaphragm is Whatman fibreglass diaphragm, in the glove box full of dry high-purity argon gas
CR2016 type button cell is dressed up in (moisture and oxygen content are both less than 0.1ppm).Button cell is placed in battery test system
On, it is tested in room temperature charge-discharge performance.In current density be 20mA/g and charging/discharging voltage range is 2.5~4.6V (vs.K+/ K) under conditions of, the second circle reversible discharge capacity is 46mAhg-1, after recycling 100 times, capacity remains 29mAh
g-1。
Case study on implementation 4:
Weigh 0.03mol ammonium metavanadate, 0.045mol ammonium phosphate, 0.04395mol potassium nitrate, 0.0105mol rubidium nitrate and
The reactants such as 0.135mol tartaric acid, and its whole is added in the beaker of 100mL, 75mL distilled water is added, it is strong to stir,
Water bath method under the conditions of 60 DEG C.Colloidal sol after being evaporated is placed in the convection oven that temperature is 160 DEG C, dry 8h.It will dry
Mixture afterwards is transferred in tube furnace, under argon atmosphere protection, is heated to 900 DEG C with the heating rate of 5 DEG C/min, constant temperature
6h cools to room temperature with the furnace to get kalium ion battery positive electrode K is arrived2.93Rb0.07V2(PO4)3/ C composite.
The kalium ion battery positive electrode K that will be prepared2.93Rb0.07V2(PO4)3/ C composite, acetylene black and PVDF
It is uniform for the ratio ground and mixed of 8:1:1 in mass ratio, suitable NMP is added dropwise, electrode slurry is made, then again by slurry in aluminium
Mill is applied on foil uniformly, is placed in 120 DEG C of vacuum ovens sufficiently dry, is cut into paillon that diameter is 15mm as Electrode,
It is compacted with twin rollers.Using the positive plate being prepared as positive electrode, using metallic potassium piece as cathode, with 0.8molL-1KPF6
PC solution as electrolyte, diaphragm is Whatman fibreglass diaphragm, in the glove box (water full of dry high-purity argon gas
Point and oxygen content be both less than 0.1ppm) in dress up CR2016 type button cell.Button cell is placed on battery test system,
It is tested in room temperature charge-discharge performance.When current density is 20mA/g and charging/discharging voltage range is 2.5~4.6V (vs.K+/K)
Under conditions of, reversible discharge capacity is 52mAhg for the first time-1, after recycling 100 times, capacity remains 30.2mAhg-1。
Case study on implementation 5:
Weigh 0.03mol ammonium metavanadate, 0.045mol ammonium phosphate, 0.04455mol potassium acetate, 0.00045mol rubidium nitrate
With the reactants such as 0.0675mol ethylenediamine tetra-acetic acid, and its whole is added in the beaker of 100mL, 80mL distilled water is added,
Strong stirring, water bath method under the conditions of 80 DEG C.Colloidal sol after being evaporated is placed in the convection oven that temperature is 160 DEG C, it is dry
8h.Mixture after drying is transferred in tube furnace, under argon atmosphere protection, is heated to the heating rate of 10 DEG C/min
1000 DEG C, constant temperature 4h, room temperature is cooled to the furnace to get kalium ion battery positive electrode K is arrived2.97Rb0.03V2(PO4)3/ C composite wood
Material.
The kalium ion battery positive electrode K that will be prepared2.97Rb0.03V2(PO4)3/ C composite, acetylene black and PVDF
It is uniform for the ratio ground and mixed of 8:1:1 in mass ratio, suitable NMP is added dropwise, electrode slurry is made, then again by slurry in aluminium
Mill is applied on foil uniformly, is placed in 120 DEG C of vacuum ovens sufficiently dry, is cut into paillon that diameter is 15mm as Electrode,
It is compacted with twin rollers.Using the positive plate being prepared as positive electrode, using metallic potassium piece as cathode, with 0.8molL-1KPF6
Polycarbonate solution as electrolyte, diaphragm is Whatman fibreglass diaphragm, in the gloves full of dry high-purity argon gas
CR2016 type button cell is dressed up in case (moisture and oxygen content are both less than 0.1ppm).Button cell is placed in battery testing system
On system, it is tested in room temperature charge-discharge performance.When current density is 20mA/g and charging/discharging voltage range is 2.5~4.6V
(vs.K+/ K) under conditions of, reversible discharge capacity is 53mAhg for the first time-1, after recycling 100 times, capacity is remained
31.5mAh·g-1。
It is numerous to list herein since embodiment of the present invention is more, without departing substantially from spirit and its essence of the invention
In the case where, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these are corresponding
Change and modification all should fall within the scope of protection of the appended claims of the present invention.
Claims (7)
1. kalium ion battery positive electrode rubidium doping phosphoric acid vanadium potassium/carbon preparation method, it is characterised in that step in detail below are as follows:
It (1) will be by vanadium source compound, P source compound, potassium resource compound, rubidium source compound, chelating agent V:P:K in molar ratio:
Rb:C=2:3:(3-x): x:6 weighs (wherein 0≤x≤0.1), and is dissolved in a certain amount of hot distilled water, heats while stirring,
Reaction after a certain period of time evaporates moisture completely, obtains blue or light green color xerogel；
(2) xerogel in (1) is dried, and the gel after drying is placed under inert atmosphere conditions, and with 2 DEG C/min~10
DEG C/heating rate of min is heated to 700 DEG C~1000 DEG C, constant temperature 4h~12h, room temperature is cooled to the furnace to get the potassium of black is arrived
Ion battery positive electrode K3-xRbxV2(PO4)3/ C composite.
2. the preparation method of kalium ion battery positive electrode rubidium doping phosphoric acid vanadium potassium/carbon according to claim 1, feature
It is, the vanadium source compound is one of vanadic anhydride, ammonium metavanadate, vanadium oxytrichloride, vanadic sulfate or a variety of.
3. the preparation method of kalium ion battery positive electrode rubidium doping phosphoric acid vanadium potassium/carbon according to claim 1, feature
It is, phosphorus source compound is ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphorus pentoxide, one in potassium dihydrogen phosphate
Kind is a variety of.
4. the preparation method of kalium ion battery positive electrode rubidium doping phosphoric acid vanadium potassium/carbon according to claim 1, feature
It is, the potassium resource compound is potassium hydroxide, potassium carbonate, saleratus, potassium nitrate, potassium acetate, one in potassium dihydrogen phosphate
Kind is a variety of.
5. the preparation method of kalium ion battery positive electrode rubidium doping phosphoric acid vanadium potassium/carbon according to claim 1, feature
It is, the rubidium source compound is one of rubidium carbonate, rubidium nitrate, rubidium acetate, rubidium sulfate, rubidium chloride, rubidium perchlorate or more
Kind.
6. the preparation method of kalium ion battery positive electrode rubidium doping phosphoric acid vanadium potassium/carbon according to claim 1, feature
It is, the chelating agent is one of citric acid, oxalic acid, tartaric acid, ethylenediamine tetra-acetic acid or a variety of.
7. the preparation method of kalium ion battery positive electrode rubidium doping phosphoric acid vanadium potassium/carbon according to claim 1, feature
It is, the inert atmosphere is one or both of nitrogen, argon gas.
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| CN112490421A (en) * | 2020-11-05 | 2021-03-12 | 西安交通大学 | Cesium-doped potassium vanadium fluorophosphate/carbon cathode material and preparation method and application thereof |
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| CN108269988A (en) * | 2018-02-01 | 2018-07-10 | 桂林理工大学 | The preparation method of sodium-ion battery positive material calcium potassium codope vanadium phosphate sodium/carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112490421A (en) * | 2020-11-05 | 2021-03-12 | 西安交通大学 | Cesium-doped potassium vanadium fluorophosphate/carbon cathode material and preparation method and application thereof |
| CN112490421B (en) * | 2020-11-05 | 2021-09-07 | 西安交通大学 | Cesium-doped potassium vanadium fluorophosphate/carbon cathode material and preparation method and application thereof |
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