CN110165189A - Kalium ion battery positive electrode magnesium doping phosphoric acid vanadium potassium/carbon composite preparation method - Google Patents
Kalium ion battery positive electrode magnesium doping phosphoric acid vanadium potassium/carbon composite preparation method Download PDFInfo
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- CN110165189A CN110165189A CN201910494006.1A CN201910494006A CN110165189A CN 110165189 A CN110165189 A CN 110165189A CN 201910494006 A CN201910494006 A CN 201910494006A CN 110165189 A CN110165189 A CN 110165189A
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- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
The invention discloses high-performance magnesium 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 magnesium doping of sol-gel method 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 magnesium and material structure is caused to change, and potassium vacancy is generated, while carbon coating improves the electronic conductivity of material, so that magnesium doping phosphoric acid vanadium potassium/carbon composite has excellent chemical property.
Description
Technical field
The invention belongs to technical field of energy material, in particular to a kind of high-performance magnesium doping phosphoric acid vanadium potassium/carbon composite wood
The preparation method of material.
Background technique
Lithium ion battery because its higher energy density, longer service life, it is light-weight and adaptable the advantages that
It is widely applied.However lithium resource reserves are few, so that lithium ion battery cost can not have always been high any more, it is difficult to large-scale application.
And it is much higher than lithium with sodium, the potassium element reserves in the earth's crust of main group with lithium, and there are physicochemical properties similar with lithium, because
This sodium-ion battery and kalium ion battery be considered as two kinds it is most possible replace lithium ion batteries and can large-scale application two
Primary cell.Compared with sodium-ion battery, since the electricity of potassium is electric to current potential lower than sodium to current potential, is conducive to kalium ion battery and possesses
Voltage more higher than sodium-ion battery and energy density.In addition to this, the K compared with Li and Na, in kalium ion battery+Louis
Acidity is weaker, compares Li to be formed+、Na+Smaller solvated ion, so that solvation K+Ionic conductivity and transfer number it is high
In Li+And Na+, while K+Desolvation energy is lower, it is easy to accomplish K+It quickly migrates, has between electrolyte/electrode interface
Conducive to polarization is reduced, the preferable high-rate performance of kalium ion battery is realized.The advantages of above-mentioned kalium ion battery, has attracted increasingly
The concern of more researchers, the further investigation with electrochmical power source researcher to kalium ion battery, kalium ion battery will
It can obtain significant progress, it will as a member important in electrochmical power source.As the important composition of battery, positive electrode becomes
The emphasis of kalium ion battery research, becomes the key of kalium ion battery development.
Kalium ion battery positive pole material phosphoric acid vanadium potassium (K3V2(PO4)3), have stable structure, operating voltage high and safety
The advantages that performance is good is a kind of great kalium ion battery positive electrode for having application prospect.But since its electronic conductivity compares
It is low and thus cause the disadvantages of activation polarization is bigger, cycle performance is poor and actual capacity is relatively low, lead to its reality
Chemical property it is poor, it is difficult to practical application.It is mainly logical at present in relation to reporting that the pertinent literature of vanadium phosphate potassium is very few
Crossing preparation has the particle of special appearance to improve the chemical property of material, and preparation method is complicated, and at high cost, the period is long, difficult
To realize industrial application.
The present invention is directed to the shortcomings that vanadium phosphate potassium and current present Research, is prepared using the sol-gel method of easy industrialization
Positive electrode, and by preparing magnesium doping phosphoric acid vanadium potassium/carbon composite in the magnesium-doped method combined with carbon coating of potassium potential
(K3-2xMgxV2(PO4)3/ C), the chemical property of vanadium phosphate potassium is significantly improved, the 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 magnesium doping phosphoric acid vanadium potassium/carbon composite, should
Method and process is simple, low in cost, and the kalium ion battery positive electrode of preparation has capacity height, has extended cycle life, high current
It can 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:
The raw material of different ratio are dissolved, kalium ion battery is being prepared just using the sol-gel method of easy industrialization
Pole material magnesium doping phosphoric acid vanadium potassium/carbon composite.Magnesium in the kalium ion battery positive electrode magnesium doping phosphoric acid vanadium potassium/carbon is mixed
Miscellaneous vanadium phosphate potassium is with K3-2xMgxV2(PO4)3It indicates, the preparation method of the positive electrode, 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:
Mg:C=2:3:(3-2x): x:6 weighs (wherein 0≤x≤0.15), and is dissolved in a certain amount of distilled water, heat and stir to
Moisture evaporation completely, obtains blue or light green color gel；
(2) gel in (1) is dried, and under inert atmosphere conditions by the xerogel after drying, 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 K3-2xMgxV2(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 magnesium source compound is one of magnesium nitrate, magnesium acetate, magnesium sulfate or a variety of；The chelating agent is lemon
One of acid, oxalic acid, tartaric acid, ethylenediamine tetra-acetic acid are a variety of；The inert atmosphere is one of nitrogen, argon gas or two
Kind.The kalium ion battery that the kalium ion battery positive electrode is assembled into is by kalium ion battery positive plate, negative electrode tab, diaphragm, electricity
Solution liquid assembles, and wherein positive plate is made after being mixed by kalium ion battery positive electrode with conductive agent and binder, negative electrode tab
For metallic potassium, diaphragm is fibreglass diaphragm, electrolyte KPF6Polycarbonate solution.
The present invention is by water-soluble substances such as vanadium source compound, P source compound, potassium resource compound, magnesium source compounds and chelates
Agent effect has powerful chelation using chelating agent, and reactant is made to reach uniformly dividing on molecular level in aqueous solution
Cloth is conducive to reaction in lower temperature and completes in the short period, and obtains 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 the vacancy that Doped ions generate potassium is introduced in potassium potential, be conducive to the deintercalation and insertion of potassium ion, from
And obtain magnesium doping phosphoric acid vanadium potassium/carbon composite of electrochemical performance.
Detailed description of the invention
Fig. 1 is the x-ray diffraction pattern of vanadium phosphate potassium prepared by case study on implementation 1 of the present invention.
Fig. 2 is the kalium ion battery positive electrode of the preparation of case study on implementation 1 of the present invention in the voltage range of 2.5~4.6V,
Current density is 20mAg-1Under the conditions of first charge-discharge curve.
Fig. 3 is the kalium ion battery positive electrode of the preparation of case study on implementation 1 of the present invention in the voltage range of 2.5~4.6V,
Current density is 20mAg-1Under the conditions of cycle performance curve.
Fig. 4 is magnesium doping phosphoric acid vanadium potassium/carbon x-ray diffraction pattern prepared by case study on implementation 2 of the present invention.
Fig. 5 is magnesium doping phosphoric acid vanadium potassium/carbon scanning electron microscope (SEM) photograph prepared by case study on implementation 2 of the present invention.
Fig. 6 is the kalium ion battery positive electrode of the preparation of case study on implementation 2 of the present invention in the voltage range of 2.5~4.6V,
Current density is 20mAg-1Under the conditions of first charge-discharge curve.
Fig. 7 is the kalium ion battery positive electrode of the preparation of case study on implementation 2 of the present invention in the voltage range of 2.5~4.6V,
Current density is 20mAg-1Under the conditions of cycle performance curve.
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 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, 0.0441mol potassium acetate,
The reactants such as 0.00045mol magnesium acetate and 0.09mol citric acid, and its whole is added in the beaker of 100mL, it is added
70mL distilled water, strong to stir, water bath method under the conditions of 80 DEG C.Colloidal sol after being evaporated is placed in the air blast that temperature is 120 DEG C
In baking oven, dry 10h.Mixture after drying is transferred in tube furnace, under argon atmosphere protection, with the liter of 2 DEG C/min
Warm rate is heated to 600 DEG C, constant temperature 8h, cools to room temperature with the furnace to get kalium ion battery positive electrode K is arrived2.94Mg0.03V2
(PO4)3/ C composite.Fig. 4 is the X-ray diffracting spectrum 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 prepared2.94Mg0.03V2(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
Coating uniformly, is placed in 120 DEG C of vacuum ovens sufficiently dry, is 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, and 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 62.3mAhg-1, after recycling 100 times, capacity is remained
32.9mAh·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 ammonium metavanadate, 0.045mol diammonium hydrogen phosphate, 0.042mol potassium acetate,
The reactants such as 0.0015mol magnesium acetate and 0.09mol citric acid, and its whole is added in the beaker of 100mL, 75mL is added
Distilled water, 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 120 DEG C
In, dry 12h.Mixture after drying is transferred in tube furnace, under argon atmosphere protection, with the heating speed of 3 DEG C/min
Rate is heated to 750 DEG C, constant temperature 9h, cools to room temperature with the furnace to get kalium ion battery positive electrode K is arrived2.8Mg0.1V2(PO4)3/C
Composite material.
The kalium ion battery positive electrode K that will be prepared2.8Mg0.1V2(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 coating 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 65mAhg-1, after recycling 100 times, capacity is remained
28.5mAh·g-1。
Case study on implementation 4:
Weigh 0.03mol ammonium metavanadate, 0.045mol ammonium phosphate, 0.0429mol potassium nitrate, 0.00105mol magnesium nitrate and
The reactants such as 0.135mol tartaric acid, and its whole is added in the beaker of 100mL, it is added in 75mL distilled water, 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 160 DEG C, dry 8h.It will do
Mixture after dry is transferred in tube furnace, under argon atmosphere protection, is heated to 900 DEG C with the heating rate of 5 DEG C/min, perseverance
Warm 6h cools to room temperature with the furnace to get kalium ion battery positive electrode K is arrived2.86Mg0.07V2(PO4)3/ C composite.
The kalium ion battery positive electrode K that will be prepared2.86Mg0.07V2(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
It is applied uniformly on foil, is placed in 120 DEG C of vacuum ovens sufficiently dry, be 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 65mAhg for the first time-1, after recycling 100 times, capacity remains 30mAhg-1。
Case study on implementation 5:
Weigh 0.03mol ammonium metavanadate, 0.045mol ammonium phosphate, 0.0441mol potassium acetate, 0.00045mol magnesium nitrate and
The reactants such as 0.0675mol ethylenediamine tetra-acetic acid, and its whole is added in the beaker of 100mL, it is added in 80mL distilled water,
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 arrived2.94Mg0.03V2(PO4)3/ C composite wood
Material.
The kalium ion battery positive electrode K that will be prepared2.94Mg0.03V2(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
It is applied uniformly on foil, is placed in 120 DEG C of vacuum ovens sufficiently dry, be 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 magnesium 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, magnesium source compound, chelating agent V:P:K in molar ratio:
Mg:C=2:3:(3-2x): x:6 weighs (wherein 0≤x≤0.15), and is dissolved in a certain amount of distilled water, then mixes this
Liquid heating, stirring simultaneously evaporate moisture completely, obtain xerogel；
(2) xerogel in (1) is dried, and the xerogel after drying is roasted under inert atmosphere conditions, with 2 DEG C/
Min~10 DEG C/min heating rate is heated to 600 DEG C~1000 DEG C, and constant temperature 4h~12h, then cools to room temperature with the furnace,
Obtain the kalium ion battery positive electrode K of black3-2xMgxV2(PO4)3/ C composite.
2. the preparation method of kalium ion battery positive electrode magnesium 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 magnesium 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 magnesium 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 magnesium doping phosphoric acid vanadium potassium/carbon according to claim 1, feature
It is, the magnesium source compound is one of magnesium nitrate, magnesium acetate, magnesium chloride, magnesium sulfate or a variety of.
6. the preparation method of kalium ion battery positive electrode magnesium 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 magnesium 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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| CN111384383A (en) * | 2020-03-25 | 2020-07-07 | 四川大学 | Coating modified nickel-based multi-element positive electrode material and preparation method thereof |
| CN111384382A (en) * | 2020-03-25 | 2020-07-07 | 四川大学 | Doping and coating dual-regulation nickel-based multi-element positive electrode material and preparation method thereof |
| CN113479860A (en) * | 2021-07-01 | 2021-10-08 | 中国石油大学(华东) | SbPO4Preparation method of/nitrogen-doped carbon composite material |
| CN114084905A (en) * | 2021-10-10 | 2022-02-25 | 中国计量大学 | Preparation method of oxygen-enriched defect potassium-embedded ammonium vanadate nanoarray cathode material |
| CN115557531A (en) * | 2022-10-11 | 2023-01-03 | 湖北工业大学 | Na containing sodium vacancies 2 Ti 3 O 7 Preparation method and application of nanorod |
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| CN111384383A (en) * | 2020-03-25 | 2020-07-07 | 四川大学 | Coating modified nickel-based multi-element positive electrode material and preparation method thereof |
| CN111384382A (en) * | 2020-03-25 | 2020-07-07 | 四川大学 | Doping and coating dual-regulation nickel-based multi-element positive electrode material and preparation method thereof |
| CN113479860A (en) * | 2021-07-01 | 2021-10-08 | 中国石油大学(华东) | SbPO4Preparation method of/nitrogen-doped carbon composite material |
| CN113479860B (en) * | 2021-07-01 | 2023-08-11 | 中国石油大学(华东) | SbPO (styrene-ethylene-propylene-diene monomer) 4 Preparation method of nitrogen-doped carbon composite material |
| CN114084905A (en) * | 2021-10-10 | 2022-02-25 | 中国计量大学 | Preparation method of oxygen-enriched defect potassium-embedded ammonium vanadate nanoarray cathode material |
| CN114084905B (en) * | 2021-10-10 | 2024-01-05 | 中国计量大学 | Preparation method of potassium-embedded ammonium vanadate nano-array positive electrode material with oxygen-enriched defect |
| CN115557531A (en) * | 2022-10-11 | 2023-01-03 | 湖北工业大学 | Na containing sodium vacancies 2 Ti 3 O 7 Preparation method and application of nanorod |
| CN115557531B (en) * | 2022-10-11 | 2023-08-04 | 湖北工业大学 | Na containing sodium vacancy 2 Ti 3 O 7 Preparation method and application of nanorods |
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