CN110474044A - A kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof - Google Patents
A kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110474044A CN110474044A CN201910840541.8A CN201910840541A CN110474044A CN 110474044 A CN110474044 A CN 110474044A CN 201910840541 A CN201910840541 A CN 201910840541A CN 110474044 A CN110474044 A CN 110474044A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- ion battery
- zinc ion
- water system
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention provides a kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof.The positive electrode has following general formula: (N, M)Σ=1V8O20·nH2O, wherein N is Li, Na, K, Zn, Cu, one of Mg or Ca, one of M Mn, Fe, Co or Ni, n 0.01-4.Above-mentioned positive electrode can be prepared by one step hydro thermal method in the present invention, and reaction condition is mild, and preparation process is simple, low for equipment requirements；The microscopic appearance of gained positive electrode is nanobelt；Gained positive electrode is applied to water system Zinc ion battery, the chemical properties such as specific discharge capacity with higher and higher cycle stability for the first time.
Description
Technical field
The present invention relates to a kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof, belong to zinc from
Sub- battery technology field.
Background technique
With the development of economy and society, the demand to high capacity, high life and high security battery is more and more urgent, nothing
By being mobile electronic device equipment or electric car field, a kind of longer working time and safer Gao Rong are required
Measure battery.
In various batteries, cathode of the Zinc ion battery using zinc as battery has high theoretical capacity (820mAh g-1),
Low redox potential, at low cost, the advantage of rich reserves, while its aqueous electrolyte further subtracts instead of organic electrolyte
Few pollution to environment and safer.Currently, the significant challenge that Zinc ion battery faces is to seek to be embedded in/take off in zinc ion
Stable structure, and the positive electrode with high capacity can be kept during out.
The zinc ion positive electrode with high capacity is mainly Mn-based material and vanadium-based materials at present.Although Mn-based material provides
Source is abundant, at low cost, but its poorly conductive, and volume change is big in charge and discharge process and generates Mn (OH)2With Zn (OH)2
By-product, and then cause its high rate performance poor, cycle life is short, hinders it and further develops.Vanadium-based materials are at low cost because of its
And its layer structure is conducive to the deintercalation of zinc ion and receives significant attention.Although vanadium-based materials have high capacity,
Most of vanadium based material is as zinc battery positive electrode in use, its stability needs to be further increased.Currently used for water system
The vanadium sub-group compound of zinc battery includes V2O5, VO2, NaV3O8·1.5H2O, LiV3O8, Na2V6O16·1.63H2O, Fe5V15O39
(OH)9·9H2O, Zn3V2O7(OH)2·2H2O.Have in the prior art by by metal cation be embedded in vanadic anhydride come
It is improved as the stability of Zinc ion battery positive electrode and the report of capacity.Such as Zn0.25V2O5·nH2O[1]In
Under the current density of 0.05A/g, capacity is 300mAh g-1；Na0.33V2O5 [2]Under the current density of 0.2A/g, capacity is
253.7mAh g-1； Ca0.25V2O5·nH2O[3]Under the current density of 0.05A/g, capacity is 340mAh g-1.But above-mentioned material
Expect that the chemical property used as Zinc ion battery positive electrode is still to be improved.
In general, developing new positive electrode is still the key for improving water system zinc battery performance, to zinc battery future
Practical application will have profound influence.Currently, for NaV8O20Anode of the equal series compounds as water system Zinc ion battery
Material has not been reported.
Summary of the invention
The present invention provides a kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof.System of the present invention
Preparation Method is simple, and the microscopic appearance of gained positive electrode is nanobelt；Gained positive electrode is applied to water system Zinc ion battery, tool
There are the chemical properties such as higher specific discharge capacity and higher cycle stability.
Technical scheme is as follows:
A kind of high-performance water system Zinc ion battery positive electrode has following general formula: (N, M)∑=1V8O20·nH2O, wherein N
For Li, Na, K, Zn, Cu, one of Mg or Ca, one of M Mn, Fe, Co or Ni, n 0.01-4.In above-mentioned general formula,
" ∑=1 " refers to that the total atom number of metallic element N and M are 1.
Preferred according to the present invention, the N in general formula is one of Na, K, Li, Zn or Ca.
Preferred according to the present invention, the microscopic appearance of the positive electrode is nanobelt, and the length of nanobelt is 0.2-1.5
μm, width 60-120nm.
The preparation method of above-mentioned high-performance water system Zinc ion battery positive electrode, comprising steps of
Weigh V2O5, the water soluble salt of metal N and the water soluble salt of metal M be well-dispersed in water, obtain mixed liquor；Use second
The pH to 1-4 of aqueous acid adjusting mixed liquor；Then the hydro-thermal reaction 12-72h at 90-200 DEG C；Be centrifuged or be filtered, washed,
It is dried to obtain water system Zinc ion battery positive electrode；The M in N in M, metal N and positive electrode general formula in above-mentioned metal M,
N has the same meaning, one of M Mn, Fe, Co or Ni, one of N Li, Na, K, Zn, Mg, Cu or Ca.
Preferred according to the present invention, the water soluble salt of metal N is sulfate, nitrate or the chlorate of metal N；Metal M
Water soluble salt be metal M sulfate or nitrate.
It is preferred according to the present invention, one kind of N Na, K, Li, Zn or Ca.
It is preferred according to the present invention, be 0.5-25: 0.5-15 by the molar ratio of metal M element, vanadium, metal N element:
7 weigh the water soluble salt of metal M, V2O5, metal N water soluble salt；Preferably, by metal M element, vanadium, metal N element
Molar ratio be 1-20: 1-13: 7 water soluble salts for weighing metal M, V2O5, metal N water soluble salt.
It is preferred according to the present invention, in the mixed liquor, V2O5Concentration be 0.1mol/L-0.7mol/L.
Preferred according to the present invention, the mass fraction of the acetic acid aqueous solution is 36-38%.
Preferred according to the present invention, the hydrothermal temperature is 120 DEG C -190 DEG C, and the reaction time is -72h for 24 hours；It is preferred that
, the hydrothermal temperature is 180 DEG C, reaction time 72h.
Preferred according to the present invention, the washing is washed with deionized water or dehydrated alcohol.
Preferred according to the present invention, the drying is to be dried in vacuo 8-20h at 40-90 DEG C；Preferably, the drying is
12h is dried in vacuo at 60 DEG C.Drying temperature needs to be suitable for that the excessively high structure that can destroy positive electrode of drying temperature causes it
Chemical property is greatly lowered.
The application of above-mentioned high-performance water system Zinc ion battery positive electrode is applied to chargeable water system zinc as positive electrode
Ion battery.
According to the present invention, positive electrode be applied to prepare chargeable water system Zinc ion battery can be by the prior art；Preferably,
Positive electrode be applied to prepare chargeable water system Zinc ion battery comprising steps of
(1) preparation of anode electrode piece
By positive electrode, active carbon and the Kynoar being dissolved in N-Methyl pyrrolidone (PVDF) are uniformly mixed
Slurry is formed, is coated on the titanium foil with a thickness of 20 μm, coating layer thickness is 200-600 μm, is dried to obtain anode electrode piece；It is described
The mass ratio of positive electrode, active carbon and Kynoar is 7: 1.5: 1.5；
(2) preparation of negative electricity pole piece
Cathode is zinc foil, with a thickness of 20-100 μm, through polishing except oxide layer, ethanol washing, dry obtained negative electrode
Piece；
(3) preparation of electrolyte
Trifluoromethayl sulfonic acid zinc is dissolved in deionized water, electrolyte is made；Trifluoromethayl sulfonic acid zinc is dense in electrolyte
Degree is 0.2-1.5g/mL；
(4) preparation of battery
Electrode slice is put into battery case, fibreglass diaphragm is put among positive and negative anodes electrode slice and separates, 50-80 μ L is added
Chargeable water system Zinc ion battery is made then to cell package in electrolyte.
According to the present invention, in step (1), the additional amount of N-Methyl pyrrolidone presses the prior art.
Technical characterstic of the invention and the utility model has the advantages that
1, the preparation method of positive electrode of the present invention is simple, only need to carry out simple hydro-thermal reaction, control the reaction time
Final positive electrode can be prepared with temperature and drying temperature；Reaction condition of the present invention is mild, and preparation process is simple,
It is low for equipment requirements；Gained positive electrode has specific structure, and microscopic appearance is nanobelt.
2, cathode abundant raw material used in water system Zinc ion battery of the present invention, it is cheap；Electrolyte is trifluoromethayl sulfonic acid
Zinc preferably inhibits the growth of cathode dendrite compared to alkaline electrolyte, and can guarantee high coulombic efficiency.Anode of the invention
The Zinc ion battery that material is prepared has higher first discharge specific capacity and cyclical stability, and has preferable forthright again
Energy；First discharge specific capacity is up to 350mAh g under the current density of 0.1A/g-1More than；Under the current density of 4A/g,
Specific discharge capacity conservation rate is up to 98% after 1000 circulations.
3, the present invention is to NaV8O20、KV8O20、LiV8O20Equal series compounds doping metals cation M ion, metal sun from
Sub- M ion doping does not significantly change their phase structure, and the doping of metal cation M ion not only expands crystal structure
Interlamellar spacing is conducive to the insertion of zinc ion, and serves as the effect of " pillar " in interlayer, improves material in charge and discharge process
The stability of structure, to realize high capacity and high circulation stability, the application for the following water system zinc battery provides tool
There is the positive electrode of application prospect.
Detailed description of the invention
Fig. 1 is Zinc ion battery positive electrode (Na, Mn) prepared by embodiment 1∑=1V8O20·nH2The X-ray diffraction of O
(XRD) map.
Fig. 2 is Zinc ion battery positive electrode (Na, Mn) prepared by embodiment 1∑=1V8O20·nH2The scanning electron of O is aobvious
Micro mirror (SEM) figure.
Fig. 3 is Zinc ion battery positive electrode (Na, Mn) prepared by embodiment 1∑=1V8O20·nH2O is in the permanent electricity of 0.1A/g
The initial charge/discharge curve flowed down.
Fig. 4 is Zinc ion battery positive electrode (Na, Mn) prepared by embodiment 1∑=1V8O20·nH2O is in 4A/g constant current
Under cycle performance figure.
Fig. 5 is Zinc ion battery positive electrode (K, Mn) prepared by embodiment 5∑=1V8O20·nH2O is in 4A/g constant current
Under cycle performance figure.
Fig. 6 is Zinc ion battery positive electrode (Li, Mn) prepared by embodiment 6∑=1V8O20·nH2O is in 4A/g constant current
Under cycle performance figure.
Fig. 7 is Zinc ion battery positive electrode (Zn, Mn) prepared by embodiment 7∑=1V8O20·nH2O is in 4A/g constant current
Under cycle performance figure.
Specific embodiment
The present invention is described further combined with specific embodiments below, but not limited to this.
Experimental method described in following embodiments is unless otherwise specified conventional method simultaneously；The reagent, material
And equipment commercially obtains unless otherwise specified.
Embodiment 1
A kind of high-performance water system Zinc ion battery positive electrode (Na, Mn)∑=1V8O20·0.04H2The preparation method of O, including
Step:
According to manganese element: vanadium: the molar ratio of sodium element weighs manganese sulfate, vanadic anhydride and sulfuric acid for 1: 13: 7
Weighed raw material is well-dispersed in 50mL water and stirs 30min, obtains mixed liquor by sodium；The matter of vanadic anhydride in mixed liquor
Amount concentration is 0.55mol/L.It is 2.5 that the acetic acid aqueous solution for being 37% with mass fraction, which adjusts pH,.It transfers the solution into have and gather
In the reaction kettle of tetrafluoroethene liner, and reaction kettle is placed in baking oven, hydro-thermal reaction 72h, is centrifuged hydro-thermal at 180 DEG C
Sediment after reaction, dehydrated alcohol washing are obtaining Zinc ion battery just after vacuum drying 12h under the conditions of temperature is 60 DEG C
Pole material.
By above-mentioned gained positive electrode be applied to prepare chargeable water system Zinc ion battery comprising steps of
(1) preparation of anode electrode piece
By the positive electrode of preparation, active carbon and Kynoar (PVDF) mixing for being dissolved in N-Methyl pyrrolidone
It is formed uniformly slurry, is coated on the titanium foil with a thickness of 20 μm, coating layer thickness is 400-600 μm, is dried to obtain anode electrode piece；
The mass ratio of the positive electrode, active carbon and Kynoar is 7: 1.5: 1.5；
(2) preparation of negative electricity pole piece
Cathode is zinc foil, with a thickness of 20 μm, removes oxide layer with sand paper polishing, is then rinsed well with ethyl alcohol, dry system
Obtain negative electricity pole piece.
(3) preparation of electrolyte
It weighs 5.4g trifluoromethayl sulfonic acid zinc and is dissolved in 5ml deionized water obtained electrolyte.
(4) preparation of battery
Electrode slice is put into battery case, fibreglass diaphragm is put among positive and negative anodes electrode slice and separates, 80 μ L electricity are added
It solves liquid and chargeable water system Zinc ion battery is made then to cell package.
X-ray diffraction (XRD) map of Zinc ion battery positive electrode manufactured in the present embodiment is as shown in Figure 1, by XRD
Analyzing its structure is (Na, Mn)∑=1V8O20·nH2O, Zinc ion battery positive electrode manufactured in the present embodiment compare NaV8O20Object
It is not very big for mutually changing, and individual interplanar distances can slightly have change.
Scanning electron microscope (SEM) figure of Zinc ion battery positive electrode manufactured in the present embodiment is as shown in Fig. 2, in figure
It can be seen that gained positive electrode microscopic appearance be nanobelt, 0.3-1 μm of length, width 80-100nm.
Head of the Zinc ion battery of Zinc ion battery positive electrode assembling manufactured in the present embodiment under 0.1A/g constant current
Charging and discharging curve is enclosed as shown in figure 3, first circle specific discharge capacity is 353.9mAh g with active substances in cathode materials Mass Calculation-1,
Illustrate that positive electrode of the present invention is applied to Zinc ion battery and has biggish specific capacity.
Circulation of the Zinc ion battery of Zinc ion battery positive electrode assembling manufactured in the present embodiment under 4A/g constant current
Performance map is as shown in figure 4, initial discharge specific capacity is 145.9mAh g-1, after the circle of circulation 500, specific discharge capacity conservation rate is
95%；After 1000 circle of circulation, for capacity retention ratio 86%, coulombic efficiency maintains always 100% or so；Illustrate the present invention just
Pole material, which is applied to Zinc ion battery, has preferable cyclical stability.
The Zinc ion battery high rate performance of Zinc ion battery positive electrode assembling manufactured in the present embodiment is good, in 0.1A/g
Current density under specific discharge capacity be 353.9mAh g-1, specific discharge capacity is 329mAh g under the current density of 0.2A/g-1, specific discharge capacity is 290mAh g under the current density of 0.5A/g-1, specific discharge capacity is under the current density of 1A/g
250mAh g-1, specific discharge capacity is 205mAh g under the current density of 2A/g-1, discharge ratio under the current density of 4A/g
Capacity is 145.9mAh g-1。
Embodiment 2
A kind of high-performance water system Zinc ion battery positive electrode (Na, Mn)∑=1V8O20·nH2The preparation of O (n 0.01-4)
Method, comprising steps of
According to manganese element: vanadium: the molar ratio of sodium element weighs manganese sulfate, vanadic anhydride and sodium sulphate for 1: 1: 7,
Weighed raw material is well-dispersed in 50mL water and stirs 30min, obtains mixed liquor；The quality of vanadic anhydride is dense in mixed liquor
Degree is 0.55mol/L.It is 2.5 that the acetic acid aqueous solution for being 36% with mass fraction, which adjusts pH,.It transfers the solution into polytetrafluoro
In the reaction kettle of ethylene liner, and reaction kettle is placed in baking oven, hydro-thermal reaction 72h, is centrifuged hydro-thermal reaction at 180 DEG C
Sediment afterwards, dehydrated alcohol washing obtain the anode of Zinc ion battery after lower vacuum drying 12h under the conditions of temperature is 60 DEG C
Material.
Above-mentioned gained positive electrode is applied to prepare chargeable water system Zinc ion battery, step is as described in Example 1.
Positive electrode obtained by the present embodiment also shows very high specific discharge capacity and cyclical stability, in the electricity of 4A/g
Under current density, initial discharge specific capacity is 149.5mAh g-1, and capacity keeps 98% after circulation 500 times, is held after circulation 1000 times
Conservation rate is measured 91%.
The high rate performance of positive electrode obtained by the present embodiment is good, and specific discharge capacity is under the current density of 0.1A/g
358.4mAh g-1, specific discharge capacity is 312mAh g under the current density of 0.2A/g-1, transferred in the current density of 0.5A/g
Electric specific capacity is 273mAh g-1, specific discharge capacity is 241mAh g under the current density of 1A/g-1, close in the electric current of 2A/g
Spending lower specific discharge capacity is 199mAh g-1, specific discharge capacity is 149.5mAh g under the current density of 4A/g-1。
Embodiment 3
A kind of high-performance water system Zinc ion battery positive electrode (Na, Mn)∑=1V8O20·nH2The preparation of O (n 0.01-4)
Method, comprising steps of
According to manganese element: vanadium: the molar ratio of sodium element weighs manganese sulfate, vanadic anhydride and sulfuric acid for 20: 13: 7
Weighed raw material is well-dispersed in 50mL water and stirs 30min, obtains mixed liquor by sodium；The matter of vanadic anhydride in mixed liquor
Amount concentration is 0.55mol/L.It is 2.5 that the acetic acid aqueous solution for being 38% with mass fraction, which adjusts pH,.It transfers the solution into have and gather
In the reaction kettle of tetrafluoroethene liner, and reaction kettle is placed in baking oven, hydro-thermal reaction 72h, is centrifuged hydro-thermal at 180 DEG C
Sediment after reaction, dehydrated alcohol washing obtain Zinc ion battery after lower vacuum drying 12h under the conditions of temperature is 60 DEG C
Positive electrode.
Above-mentioned gained positive electrode is applied to prepare chargeable water system Zinc ion battery, step is as described in Example 1.
Positive electrode obtained by the present embodiment has very high specific discharge capacity and cyclical stability, close in the electric current of 4A/g
Under degree, initial discharge specific capacity is 151mAh g-1, capacity retention ratio is 99% after recycling 500 times, and capacity is protected after circulation 1000 times
Holdup is still up to 98%.
Positive electrode high rate performance obtained by the present embodiment is good, and specific discharge capacity is under the current density of 0.1A/g
351.2mAh g-1, specific discharge capacity is 318mAh g under the current density of 0.2A/g-1, transferred in the current density of 0.5A/g
Electric specific capacity is 286mAh g-1, specific discharge capacity is 247mAh g under the current density of 1A/g-1, in the current density of 2A/g
Lower specific discharge capacity is 202mAh g-1, specific discharge capacity is 151mAh g under the current density of 4A/g-1。
Positive electrode (Na, Mn) of the invention∑=1V8O20·nH2O, different Mn dopings are not for the change of capacity
It is very big, mainly improve the stability during charge and discharge cycles.Because adulterating pillar of the Mn as crystal structure, improve
The stability of structure during charge and discharge cycles.
Embodiment 4
A kind of high-performance water system Zinc ion battery positive electrode (K, Mn)∑=1V8O20·nH2The preparation side of O (n 0.01-4)
Method, comprising steps of
According to manganese element: vanadium: the molar ratio of potassium element weighs manganese sulfate, vanadic anhydride and sulfuric acid for 1: 13: 7
Weighed raw material is well-dispersed in 50mL water and stirs 30min, obtains mixed liquor by potassium；The matter of vanadic anhydride in mixed liquor
Amount concentration is 0.55mol/L.It is 2.5 that the acetic acid aqueous solution for being 36% with mass fraction, which adjusts pH,.It transfers the solution into have and gather
In the reaction kettle of tetrafluoroethene liner, and reaction kettle is placed in baking oven, hydro-thermal reaction 72h, is centrifuged hydro-thermal at 180 DEG C
Sediment after reaction, dehydrated alcohol washing obtain Zinc ion battery after lower vacuum drying 12h under the conditions of temperature is 60 DEG C
Positive electrode.
Above-mentioned gained positive electrode is applied to prepare chargeable water system Zinc ion battery, step is as described in Example 1.
Zinc ion battery positive electrode (K, Mn) manufactured in the present embodiment∑=1V8O20·nH2O following under 4A/g constant current
Ring performance map as shown in figure 5, have very high specific discharge capacity and cyclical stability, in the current density of 4A/g as seen from the figure
Under, initial discharge specific capacity is 84.2mAh g-1, specific discharge capacity is 145.8mAh g after recycling 500 times-1, material is in charge and discharge
The initial stage of electricity, there are activation processs, so that capacity improves, specific discharge capacity is 142.3mAh g after circulation 1000 times-1。
Zinc ion battery positive electrode high rate performance manufactured in the present embodiment is good, discharges under the current density of 0.1A/g
Specific capacity is 301.6mAh g-1, specific discharge capacity is 278mAh g under the current density of 0.2A/g-1, in the electric current of 0.5A/g
Specific discharge capacity is 231mAh g under density-1, specific discharge capacity is 202mAh g under the current density of 1A/g-1, 2A/g's
Specific discharge capacity is 177mAh g under current density-1, specific discharge capacity is 140mAh g under the current density of 4A/g-1。
Embodiment 5
A kind of high-performance water system Zinc ion battery positive electrode (Li, Mn)∑=1V8O20·nH2The preparation of O (n 0.01-4)
Method, comprising steps of
According to manganese element: vanadium: the molar ratio of elemental lithium weighs manganese sulfate, vanadic anhydride and sulfuric acid for 1: 13: 7
Weighed raw material is well-dispersed in 50mL water and stirs 30min, obtains mixed liquor by lithium；The matter of vanadic anhydride in mixed liquor
Amount concentration is 0.55mol/L.It is 2.5 that the acetic acid aqueous solution for being 36% with mass fraction, which adjusts pH,.It transfers the solution into have and gather
In the reaction kettle of tetrafluoroethene liner, and reaction kettle is placed in baking oven, hydro-thermal reaction 72h, is centrifuged hydro-thermal at 180 DEG C
Sediment after reaction, dehydrated alcohol washing obtain Zinc ion battery after lower vacuum drying 12h under the conditions of temperature is 60 DEG C
Positive electrode.
Above-mentioned gained positive electrode is applied to prepare chargeable water system Zinc ion battery, step is as described in Example 1.
Zinc ion battery positive electrode (Li, Mn) manufactured in the present embodiment∑=1V8O20·nH2O following under 4A/g constant current
Ring performance map as shown in fig. 6, have very high specific discharge capacity and cyclical stability, in the current density of 4A/g as seen from the figure
Under, initial discharge specific capacity is 143.4mAh g-1, capacity retention ratio is 85% after recycling 500 times, and capacity is protected after circulation 1000 times
Holdup is 77%.
Zinc ion battery positive electrode high rate performance manufactured in the present embodiment is good, discharges under the current density of 0.1A/g
Specific capacity is 345.3mAh g-1, specific discharge capacity is 309mAh g under the current density of 0.2A/g-1, in the electric current of 0.5A/g
Specific discharge capacity is 271mAh g under density-1, specific discharge capacity is 236mAh g under the current density of 1A/g-1, 2A/g's
Specific discharge capacity is 194mAh g under current density-1, specific discharge capacity is 143.4mAh g under the current density of 4A/g-1。
Embodiment 6
A kind of high-performance water system Zinc ion battery positive electrode (Zn, Mn)∑=1V8O20·nH2The preparation of O (n 0.01-4)
Method, comprising steps of
According to manganese element: vanadium: the molar ratio of Zn-ef ficiency weighs manganese sulfate, vanadic anhydride and sulfuric acid for 1: 13: 7
Weighed raw material is well-dispersed in 50mL water and stirs 30min, obtains mixed liquor by zinc；The matter of vanadic anhydride in mixed liquor
Amount concentration is 0.55mol/L.It is 2.5 that the acetic acid aqueous solution for being 36% with mass concentration, which adjusts pH,.It transfers the solution into have and gather
In the reaction kettle of tetrafluoroethene liner, and reaction kettle is placed in baking oven, hydro-thermal reaction 72h, is centrifuged hydro-thermal at 180 DEG C
Sediment after reaction, dehydrated alcohol washing obtain Zinc ion battery after lower vacuum drying 12h under the conditions of temperature is 60 DEG C
Positive electrode.
Above-mentioned gained positive electrode is applied to prepare chargeable water system Zinc ion battery, step is as described in Example 1.
Zinc ion battery positive electrode (Zn, Mn) manufactured in the present embodiment∑=1V8O20·nH2O following under 4A/g constant current
Ring performance map has very high specific discharge capacity and cyclical stability as shown in fig. 7, as seen from the figure, close in the electric current of 4A/g
Under degree, initial discharge specific capacity is 144.6mAh g-1, capacity retention ratio is 95% after recycling 500 times, capacity after circulation 1000 times
Conservation rate is 90%.
The high rate performance of Zinc ion battery positive electrode manufactured in the present embodiment is good, transfers in the current density of 0.1A/g
Electric specific capacity is 357.7mAh g-1, specific discharge capacity is 323mAh g under the current density of 0.2A/g-1, in the electricity of 0.5A/g
Specific discharge capacity is 279mAh g under current density-1, specific discharge capacity is 243mAh g under the current density of 1A/g-1, in 2A/g
Current density under specific discharge capacity be 211mAh g-1, specific discharge capacity is 144.6mAh g under the current density of 4A/g-1。
Embodiment 7
A kind of high-performance water system Zinc ion battery positive electrode (Ca, Mn)∑=1V8O20·nH2The preparation of O (n 0.01-4)
Method, comprising steps of
According to manganese element: vanadium: the molar ratio of calcium constituent weighs manganese sulfate, vanadic anhydride and calcium chloride for 1: 13: 7
Or calcium nitrate, weighed raw material is well-dispersed in 50mL water and stirs 30min, obtains mixed liquor；Five oxidation two in mixed liquor
The mass concentration of vanadium is 0.55mol/L.It is 2.5 that the acetic acid aqueous solution for being 36% with mass concentration, which adjusts pH,.It transfers the solution into
In reaction kettle with polytetrafluoroethyllining lining, and reaction kettle is placed in baking oven, hydro-thermal reaction 72h at 180 DEG C, through centrifugation point
From the sediment after hydro-thermal reaction, dehydrated alcohol washing obtains zinc ion electricity under the conditions of temperature is 60 DEG C after vacuum drying 12h
The positive electrode in pond.
Above-mentioned gained positive electrode is applied to prepare chargeable water system Zinc ion battery, step is as described in Example 1.
Zinc ion battery positive electrode (Ca, Mn) manufactured in the present embodiment∑=1V8O20·nH2Current density of the O in 4A/g
Under, initial discharge specific capacity is 127.9mAh g-1, capacity retention ratio is 97% after recycling 500 times.
Embodiment 8
A kind of high-performance water system Zinc ion battery positive electrode (Na, Fe)∑=1V8O20·nH2The preparation of O (n 0.01-4)
Method, comprising steps of
According to ferro element: vanadium: the molar ratio of sodium element weighs ferric sulfate, vanadic anhydride and sulfuric acid for 1: 13: 7
Weighed raw material is well-dispersed in 50mL water and stirs 30min, obtains mixed liquor by sodium；The matter of vanadic anhydride in mixed liquor
Amount concentration is 0.55mol/L.It is 2.5 that the acetic acid aqueous solution for being 36% with mass concentration, which adjusts pH,.It transfers the solution into have and gather
In the reaction kettle of tetrafluoroethene liner, and reaction kettle is placed in baking oven, hydro-thermal reaction 72h, is centrifuged hydro-thermal at 180 DEG C
Sediment after reaction, dehydrated alcohol washing obtain Zinc ion battery after lower vacuum drying 12h under the conditions of temperature is 60 DEG C
Positive electrode.
Above-mentioned gained positive electrode is applied to prepare chargeable water system Zinc ion battery, step is as described in Example 1.
Zinc ion battery positive electrode (Na, Fe) manufactured in the present embodiment∑=1VaO20·nH2Current density of the O in 4A/g
Under, initial discharge specific capacity is 149.3mAh g-1, capacity retention ratio is 91% after recycling 500 times.
Embodiment 9
A kind of high-performance water system Zinc ion battery positive electrode (Na, Co)∑=1V8O20·nH2The preparation of O (n 0.01-4)
Method, comprising steps of
According to cobalt element: vanadium: the molar ratio of sodium element weighs cobalt nitrate, vanadic anhydride and sulfuric acid for 1: 13: 7
Weighed raw material is well-dispersed in 50mL water and stirs 30min, obtains mixed liquor by sodium；The matter of vanadic anhydride in mixed liquor
Amount concentration is 0.55mol/L.It is 2.5 that the acetic acid aqueous solution for being 36% with mass concentration, which adjusts pH,.It transfers the solution into have and gather
In the reaction kettle of tetrafluoroethene liner, and reaction kettle is placed in baking oven, hydro-thermal reaction 72h, is centrifuged hydro-thermal at 180 DEG C
Sediment after reaction, dehydrated alcohol washing obtain Zinc ion battery after lower vacuum drying 12h under the conditions of temperature is 60 DEG C
Positive electrode.
Above-mentioned gained positive electrode is applied to prepare chargeable water system Zinc ion battery, step is as described in Example 1.
Zinc ion battery positive electrode (Na, Co) manufactured in the present embodiment∑=1V8O20·nH2Current density of the O in 4A/g
Under, initial discharge specific capacity is 165.2mAh g-1, capacity retention ratio is 90% after recycling 500 times.
Embodiment 10
A kind of high-performance water system Zinc ion battery positive electrode (Na, Ni)∑=1V8O20·nH2The preparation of O (n 0.01-4)
Method, comprising steps of
According to nickel element: vanadium: the molar ratio of sodium element weighs nickel sulfate, vanadic anhydride and sulfuric acid for 1: 13: 7
Weighed raw material is well-dispersed in 50mL water and stirs 30min, obtains mixed liquor by sodium；The matter of vanadic anhydride in mixed liquor
Amount concentration is 0.55mol/L.It is 2.5 that the acetic acid aqueous solution for being 36% with mass concentration, which adjusts pH,.It transfers the solution into have and gather
In the reaction kettle of tetrafluoroethene liner, and reaction kettle is placed in baking oven, hydro-thermal reaction 72h, is centrifuged hydro-thermal at 180 DEG C
Sediment after reaction, dehydrated alcohol washing obtain Zinc ion battery after lower vacuum drying 12h under the conditions of temperature is 60 DEG C
Positive electrode.
Above-mentioned gained positive electrode is applied to prepare chargeable water system Zinc ion battery, step is as described in Example 1.
Zinc ion battery positive electrode (Na, Ni) manufactured in the present embodiment∑=1V8O20·nH2Current density of the O in 4A/g
Under, initial discharge specific capacity is 179mAh g-1, capacity retention ratio is 88% after recycling 500 times.
Comparative example 1
A kind of water system Zinc ion battery positive electrode NaV8O20·nH2The preparation method of O (n 0.01-4), comprising steps of
According to vanadium: the molar ratio of sodium element is 13: 7, vanadic anhydride and sodium sulphate is weighed, by weighed raw material
It is well-dispersed in 50mL water and stirs 30min, obtain mixed liquor；The mass concentration of vanadic anhydride is 0.55mol/L in mixed liquor.
It is 2.5 that the acetic acid aqueous solution for being 37% with mass fraction, which adjusts pH,.Transfer the solution into the reaction with polytetrafluoroethyllining lining
In kettle, and reaction kettle is placed in baking oven, hydro-thermal reaction 72h at 180 DEG C, the sediment after being centrifuged hydro-thermal reaction, nothing
Water-ethanol washing obtains the positive electrode of Zinc ion battery after vacuum drying 12h under the conditions of temperature is 60 DEG C.
Above-mentioned gained positive electrode is applied to prepare chargeable water system Zinc ion battery, step is as described in Example 1.
The Zinc ion battery positive electrode NaV of this comparative example preparation8O20·nH2O battery performance is poor, in the electric current of 4A/g
Under density, initial discharge specific capacity is 125mAh g-1, capacity retention ratio is 75% after recycling 500 times, capacity after circulation 1000 times
Conservation rate is only 69%.High rate performance is general, and specific discharge capacity is 308mAh g under the current density of 0.1A/g-1, in 0.2A/
Specific discharge capacity is 269mAh g under the current density of g-1, specific discharge capacity is 237mAh g under the current density of 0.5A/g-1, specific discharge capacity is 203mAh g under the current density of 1A/g-1, specific discharge capacity is under the current density of 2A/g
147mAh g-1, specific discharge capacity is 125mAh g under the current density of 4A/g-1。
By comparing it is found that NaV8O20·nH2Stability, capacity and the high rate performance of O is all not so good as the embodiment of the present invention
1.Because of NaV8O20·nH2O results in its poor stability and capacity etc. the phenomenon that Na has dissolution in charge and discharge process,
And the embodiment of the present invention 1 improves the stability and capacity of crystal structure in charge and discharge process by doping Mn.
Comparative example 2
A kind of high-performance water system Zinc ion battery positive electrode (Na, Mn)∑=1V8O20·nH2The preparation of O (n 0.01-4)
Method, comprising steps of
According to manganese element: vanadium: the molar ratio of sodium element weighs manganese sulfate, vanadic anhydride and sulfuric acid for 1: 13: 7
Weighed raw material is well-dispersed in 50mL water and stirs 30min, obtains mixed liquor by sodium；The matter of vanadic anhydride in mixed liquor
Amount concentration is 0.55mol/L.It is 2.5 that the acetic acid aqueous solution for being 37% with mass fraction, which adjusts pH,.It transfers the solution into have and gather
In the reaction kettle of tetrafluoroethene liner, and reaction kettle is placed in baking oven, hydro-thermal reaction 72h, is centrifuged hydro-thermal at 180 DEG C
Sediment after reaction, dehydrated alcohol washing obtain Zinc ion battery after vacuum drying 12h under the conditions of temperature is 120 DEG C
Positive electrode.
Above-mentioned gained positive electrode is applied to prepare chargeable water system Zinc ion battery, step is as described in Example 1.
Positive electrode battery performance obtained by this comparative example is poor, and under the current density of 4A/g, initial discharge specific capacity is
140mAh g-1, capacity keeps 50% after recycling 500 times, and capacity retention ratio is 20% after 1000 circle of circulation.Change vacuum drying temperature
The cyclical stability of degree gained positive electrode can not show a candle to the embodiment of the present invention 1.
The part electrical performance data comparison of the embodiment of the present invention and the positive electrode of comparative example preparation is as shown in the table:
1 part electrical performance data contrast table of table
Can intuitively it be found out by upper table data, present invention gained positive electrode specific discharge capacity with higher and preferable
Cyclical stability.
Bibliography:
[1] Kundu, D.；Adams, B.D.；Duffort, V.；Vajargah, S.H.；Nazar, L.F.A High-
Capacity and Long-LifeAqueous Rechargeable Zinc Battery Using a Metal Oxide
Intercalation Cathode.Nat. Energy 2016,1 (10), 16119.
[2] He, P.；Zhang, G.；Liao, X.；Yan, M.；Xu, X.；An, Q.；Liu, J.；Mai, L.Sodium Ion
Stabilized Vanadium Oxide Nanowire Cathodefor High-Performance Zinc-Ion
Batteries.Adv.Energy Mater. 2018,8 (10), 1702463.
[3] Xia, C.；Guo, J.；Li, P.；Zhang, X.；Alshareef, H.N.Highly Stable Aqueous
Zinc-Ion Storage Using a Layered Calcium Vanadium Oxide Bronze
Cathode.Angew.Chem., Int.Ed.2018,57 (15), 3943-3948.
Claims (10)
1. a kind of high-performance water system Zinc ion battery positive electrode has following general formula: (N, M)Σ=1V8O20·nH2O, wherein N be
One of Li, Na, K, Zn, Cu, Mg or Ca, one of M Mn, Fe, Co or Ni, n 0.01-4.
2. high-performance water system Zinc ion battery positive electrode according to claim 1, which is characterized in that N in general formula be Na,
K, Li, Zn or Ca.
3. high-performance water system Zinc ion battery positive electrode according to claim 1, which is characterized in that the positive electrode
Microscopic appearance is nanobelt, and the length of nanobelt is 0.2-1.5 μm, width 60-120nm.
4. the preparation method of high-performance water system Zinc ion battery positive electrode as described in any one of claims 1-3, including step
It is rapid:
Weigh V2O5, the water soluble salt of metal N and the water soluble salt of metal M be well-dispersed in water, obtain mixed liquor；With acetic acid water
The pH to 1-4 of solution adjusting mixed liquor；Then the hydro-thermal reaction 12-72h at 90-200 DEG C；It is centrifuged or is filtered, washed, dried
Obtain water system Zinc ion battery positive electrode；The metal M is one of Mn, Fe, Co or Ni, metal N is Li, Na, K, Zn,
One of Mg, Cu or Ca.
5. the preparation method of high-performance water system Zinc ion battery positive electrode according to claim 4, which is characterized in that including
It is one or more in the following conditions:
A, metal N is one of Na, K, Li, Zn or Ca；
B, the water solubility of metal M is weighed for 0.5-25:0.5-15:7 by the molar ratio of metal M element, vanadium, metal N element
Salt, V2O5, metal N water soluble salt；It preferably, is 1-20:1- by the molar ratio of metal M element, vanadium, metal N element
13:7 weighs the water soluble salt of metal M, V2O5, metal N water soluble salt；
C, the water soluble salt of metal N is sulfate, nitrate or the chlorate of metal N；The water soluble salt of metal M is metal M's
Sulfate or nitrate.
6. the preparation method of high-performance water system Zinc ion battery positive electrode according to claim 4, which is characterized in that including
It is one or more in the following conditions:
A, in the mixed liquor, V2O5Concentration be 0.1mol/L-0.7mol/L；
B, the mass fraction of the acetic acid aqueous solution is 36-38%.
7. the preparation method of high-performance water system Zinc ion battery positive electrode according to claim 4, which is characterized in that described
Hydrothermal temperature is 120 DEG C -190 DEG C, and the reaction time is -72h for 24 hours；Preferably, the hydrothermal temperature is 180 DEG C, instead
It is 72h between seasonable.
8. the preparation method of high-performance water system Zinc ion battery positive electrode according to claim 4, which is characterized in that described
Drying is to be dried in vacuo 8-20h at 40-90 DEG C；Preferably, the drying is to be dried in vacuo 12h at 60 DEG C.
9. the application of high-performance water system Zinc ion battery positive electrode as described in any one of claims 1-3, as positive material
Material is applied to chargeable water system Zinc ion battery.
10. the application of high-performance water system Zinc ion battery positive electrode according to claim 9 is applied to prepare chargeable
Water system Zinc ion battery comprising steps of
(1) preparation of anode electrode piece
By positive electrode, active carbon and the Kynoar being dissolved in N-Methyl pyrrolidone (PVDF) are uniformly mixed and are formed
Slurry is coated on the titanium foil with a thickness of 20 μm, and coating layer thickness is 200-600 μm, is dried to obtain anode electrode piece；The anode
The mass ratio of material, active carbon and Kynoar is 7:1.5:1.5；
(2) preparation of negative electricity pole piece
Cathode is zinc foil, with a thickness of 20-100 μm, through polishing except oxide layer, ethanol washing, dry obtained negative electricity pole piece；
(3) preparation of electrolyte
Trifluoromethayl sulfonic acid zinc is dissolved in deionized water, electrolyte is made；Trifluoromethayl sulfonic acid zinc concentration is in electrolyte
0.2-1.5g/mL；
(4) preparation of battery
Electrode slice is put into battery case, fibreglass diaphragm is put among positive and negative anodes electrode slice and separates, 50-80 μ L electrolysis is added
Chargeable water system Zinc ion battery is made then to cell package in liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910840541.8A CN110474044B (en) | 2019-09-05 | 2019-09-05 | High-performance water-based zinc ion battery positive electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910840541.8A CN110474044B (en) | 2019-09-05 | 2019-09-05 | High-performance water-based zinc ion battery positive electrode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110474044A true CN110474044A (en) | 2019-11-19 |
| CN110474044B CN110474044B (en) | 2021-07-16 |
Family
ID=68515078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910840541.8A Active CN110474044B (en) | 2019-09-05 | 2019-09-05 | High-performance water-based zinc ion battery positive electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110474044B (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111244422A (en) * | 2020-01-19 | 2020-06-05 | 山东大学 | Organic ion doped vanadium oxide positive electrode material for water-based zinc ion battery and preparation method and application thereof |
| CN111834628A (en) * | 2020-07-28 | 2020-10-27 | 湖南工学院 | Na-doped NH4V4O10Nano sheet material and preparation method and application thereof |
| CN112062160A (en) * | 2020-08-21 | 2020-12-11 | 浙江工业大学 | Preparation method and application of positive electrode material of zinc iron vanadate ion battery |
| CN112271288A (en) * | 2020-10-30 | 2021-01-26 | 西北工业大学 | Preparation method of zinc ion battery ZIB positive electrode material based on vanadium oxide |
| CN112271342A (en) * | 2020-10-30 | 2021-01-26 | 西北工业大学 | Preparation method of zinc ion battery ZIB based on vanadium oxide positive electrode material |
| CN112582610A (en) * | 2020-12-28 | 2021-03-30 | 安阳师范学院 | Flexible zinc ion battery based on conductive MOFs (metal-organic frameworks) based nano material |
| CN112635746A (en) * | 2020-12-22 | 2021-04-09 | 内蒙古大学 | Preparation method and application of water-based zinc ion battery vanadium-based positive electrode material |
| CN112670502A (en) * | 2021-01-28 | 2021-04-16 | 河南工业大学 | Antimony telluride nanosheet and application thereof in water-based zinc ion battery |
| CN113161522A (en) * | 2021-03-12 | 2021-07-23 | 广东工业大学 | Amorphous vanadium oxide/carbon composite material and preparation method and application thereof |
| CN113401941A (en) * | 2021-06-18 | 2021-09-17 | 河南科技大学 | Copper ion or bismuth ion doped vanadium oxide material and preparation method and application thereof |
| CN113415794A (en) * | 2021-06-17 | 2021-09-21 | 山东大学 | Water-based zinc battery positive electrode material prepared through phosphating process and preparation method and application thereof |
| CN113428897A (en) * | 2021-06-25 | 2021-09-24 | 湘潭大学 | Preparation method of vanadium-based cathode material based on surface modification for enhancing cycle stability |
| CN113772727A (en) * | 2021-09-06 | 2021-12-10 | 长沙学院 | Preparation method and application of iron-doped copper pyrovanadate material |
| CN113782727A (en) * | 2021-09-13 | 2021-12-10 | 厦门理工学院 | Preparation method of zinc ion battery doped positive electrode material, zinc ion battery doped positive electrode material and zinc ion battery |
| CN113979473A (en) * | 2021-10-26 | 2022-01-28 | 西安交通大学 | Preparation method of cathode material, cathode of water-based zinc ion battery and application |
| CN114084906A (en) * | 2021-11-01 | 2022-02-25 | 西北工业大学 | Rapid preparation method and application of alkali metal ion intercalation vanadium oxide nanobelt |
| CN114613983A (en) * | 2022-02-25 | 2022-06-10 | 华南师大(清远)科技创新研究院有限公司 | Preparation of vanadium-based compound electrode material and application of vanadium-based compound electrode material in water-based zinc ion battery |
| CN115036472A (en) * | 2022-05-20 | 2022-09-09 | 青岛大学 | High-performance zinc ion battery positive polyethylene oxide intercalation LiV 3 O 8 Nanosheet and preparation method |
| CN115084497A (en) * | 2022-08-23 | 2022-09-20 | 河南师范大学 | Preparation method and application of transition metal embedded layered vanadium oxide interlayer material |
| CN115084489A (en) * | 2022-08-19 | 2022-09-20 | 河南师范大学 | Preparation method and application of ultrasonic-assisted intercalation vanadium-based oxide composite material |
| CN115528238A (en) * | 2022-10-08 | 2022-12-27 | 中国石油大学(华东) | Vanadium-based positive electrode material, preparation method thereof and lithium ion battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170250449A1 (en) * | 2015-06-08 | 2017-08-31 | University Of Waterloo | Electrode Materials For Rechargeable Zinc Cells and Batteries Produced Therefrom |
| CN107221716A (en) * | 2017-05-23 | 2017-09-29 | 武汉理工大学 | A kind of chargeable water system Zinc ion battery |
| CN110048094A (en) * | 2019-03-22 | 2019-07-23 | 湘潭大学 | A kind of self-supporting laminated film and preparation method thereof for liquid phase Zinc ion battery |
-
2019
- 2019-09-05 CN CN201910840541.8A patent/CN110474044B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170250449A1 (en) * | 2015-06-08 | 2017-08-31 | University Of Waterloo | Electrode Materials For Rechargeable Zinc Cells and Batteries Produced Therefrom |
| CN107221716A (en) * | 2017-05-23 | 2017-09-29 | 武汉理工大学 | A kind of chargeable water system Zinc ion battery |
| CN110048094A (en) * | 2019-03-22 | 2019-07-23 | 湘潭大学 | A kind of self-supporting laminated film and preparation method thereof for liquid phase Zinc ion battery |
Non-Patent Citations (1)
| Title |
|---|
| YONGQIANG YANG等: ""Transition metal ion-preintercalated V2O5 as high-performance aqueous zinc-ion battery cathode with broad temperature adaptability"", 《NANO ENERGY》 * |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111244422A (en) * | 2020-01-19 | 2020-06-05 | 山东大学 | Organic ion doped vanadium oxide positive electrode material for water-based zinc ion battery and preparation method and application thereof |
| CN111244422B (en) * | 2020-01-19 | 2022-03-18 | 山东大学 | Organic ion doped vanadium oxide positive electrode material for water-based zinc ion battery and preparation method and application thereof |
| CN111834628B (en) * | 2020-07-28 | 2021-11-02 | 湖南工学院 | Na-doped NH4V4O10Nano sheet material and preparation method and application thereof |
| CN111834628A (en) * | 2020-07-28 | 2020-10-27 | 湖南工学院 | Na-doped NH4V4O10Nano sheet material and preparation method and application thereof |
| CN112062160A (en) * | 2020-08-21 | 2020-12-11 | 浙江工业大学 | Preparation method and application of positive electrode material of zinc iron vanadate ion battery |
| CN112271288A (en) * | 2020-10-30 | 2021-01-26 | 西北工业大学 | Preparation method of zinc ion battery ZIB positive electrode material based on vanadium oxide |
| CN112271342A (en) * | 2020-10-30 | 2021-01-26 | 西北工业大学 | Preparation method of zinc ion battery ZIB based on vanadium oxide positive electrode material |
| CN112271342B (en) * | 2020-10-30 | 2023-04-28 | 西北工业大学 | Preparation method of zinc ion battery ZIB based on vanadium oxide anode material |
| CN112635746A (en) * | 2020-12-22 | 2021-04-09 | 内蒙古大学 | Preparation method and application of water-based zinc ion battery vanadium-based positive electrode material |
| CN112582610A (en) * | 2020-12-28 | 2021-03-30 | 安阳师范学院 | Flexible zinc ion battery based on conductive MOFs (metal-organic frameworks) based nano material |
| CN112670502A (en) * | 2021-01-28 | 2021-04-16 | 河南工业大学 | Antimony telluride nanosheet and application thereof in water-based zinc ion battery |
| CN113161522A (en) * | 2021-03-12 | 2021-07-23 | 广东工业大学 | Amorphous vanadium oxide/carbon composite material and preparation method and application thereof |
| CN113161522B (en) * | 2021-03-12 | 2022-07-19 | 广东工业大学 | Amorphous vanadium oxide/carbon composite material and preparation method and application thereof |
| CN113415794A (en) * | 2021-06-17 | 2021-09-21 | 山东大学 | Water-based zinc battery positive electrode material prepared through phosphating process and preparation method and application thereof |
| CN113401941A (en) * | 2021-06-18 | 2021-09-17 | 河南科技大学 | Copper ion or bismuth ion doped vanadium oxide material and preparation method and application thereof |
| CN113428897A (en) * | 2021-06-25 | 2021-09-24 | 湘潭大学 | Preparation method of vanadium-based cathode material based on surface modification for enhancing cycle stability |
| CN113772727A (en) * | 2021-09-06 | 2021-12-10 | 长沙学院 | Preparation method and application of iron-doped copper pyrovanadate material |
| CN113782727A (en) * | 2021-09-13 | 2021-12-10 | 厦门理工学院 | Preparation method of zinc ion battery doped positive electrode material, zinc ion battery doped positive electrode material and zinc ion battery |
| CN113979473A (en) * | 2021-10-26 | 2022-01-28 | 西安交通大学 | Preparation method of cathode material, cathode of water-based zinc ion battery and application |
| CN114084906A (en) * | 2021-11-01 | 2022-02-25 | 西北工业大学 | Rapid preparation method and application of alkali metal ion intercalation vanadium oxide nanobelt |
| CN114613983A (en) * | 2022-02-25 | 2022-06-10 | 华南师大(清远)科技创新研究院有限公司 | Preparation of vanadium-based compound electrode material and application of vanadium-based compound electrode material in water-based zinc ion battery |
| CN115036472A (en) * | 2022-05-20 | 2022-09-09 | 青岛大学 | High-performance zinc ion battery positive polyethylene oxide intercalation LiV 3 O 8 Nanosheet and preparation method |
| CN115084489A (en) * | 2022-08-19 | 2022-09-20 | 河南师范大学 | Preparation method and application of ultrasonic-assisted intercalation vanadium-based oxide composite material |
| CN115084497A (en) * | 2022-08-23 | 2022-09-20 | 河南师范大学 | Preparation method and application of transition metal embedded layered vanadium oxide interlayer material |
| CN115528238A (en) * | 2022-10-08 | 2022-12-27 | 中国石油大学(华东) | Vanadium-based positive electrode material, preparation method thereof and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110474044B (en) | 2021-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110474044A (en) | A kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof | |
| EP3048659B1 (en) | Layered oxide material and preparation method therefor, pole piece, secondary cell and application thereof | |
| CN102201576B (en) | Porous carbon in situ composite lithium iron phosphate cathode material and preparation method thereof | |
| CN103928672B (en) | A kind of positive electrode active material for lithium ion battery and preparation method thereof | |
| CN105958131A (en) | Rechargeable water system zinc ion battery with long cycle life and high energy density | |
| CN103904321B (en) | The high-temperature solid phase preparation method of lithium ion battery negative material LiMn2O4 | |
| CN102244236A (en) | Method for preparing lithium-enriched cathodic material of lithium ion battery | |
| CN101488584A (en) | Asymmetric lithium iron phosphate cell using lithium titanate as main active substance of negative pole | |
| CN111525129A (en) | Water system sodium ion full battery based on nickel Prussian blue cathode material and preparation method and application thereof | |
| CN108933237B (en) | Preparation method and application of lithium ion battery positive electrode material | |
| CN102569773B (en) | Anode material for lithium-ion secondary battery and preparation method thereof | |
| CN107834050A (en) | A kind of lithium-enriched cathodic material of lithium ion battery and its improved method | |
| CN105692576A (en) | Method for preparing battery-grade FePO4 from industrial iron-containing waste | |
| CN114843469B (en) | MgFe 2 O 4 Modified P2/O3 type nickel-based layered sodium ion battery positive electrode material and preparation method thereof | |
| CN108807912B (en) | C @ SnOx(x=0,1,2)Preparation and application of @ C mesoporous nano hollow sphere structure | |
| CN104037412A (en) | Preparation method of multilevel-structured hollow nano-sphere of negative electrode material of high-performance lithium ion secondary battery | |
| CN114864896A (en) | In-situ carbon-coated nano lithium iron phosphate cathode material and preparation method thereof | |
| CN102838102A (en) | Preparation method of lithium iron phosphate monocrystalline nanorods | |
| CN111592045A (en) | Potassium manganate potassium ion battery anode material | |
| CN106960947A (en) | Composite, its preparation method and application | |
| CN105304895B (en) | Electricity nano-electrode material of lithium containing lithium metal oxide and preparation method thereof | |
| CN109279663B (en) | Borate sodium-ion battery negative electrode material and preparation and application thereof | |
| CN107768664A (en) | A kind of lithium-rich manganese-based anode material of molybdenum doping and preparation method thereof | |
| CN110993971A (en) | NiS2/ZnIn2S4Composite material and preparation method and application thereof | |
| CN106938852A (en) | A kind of preparation method of lithium ion battery negative material nanometer CuO |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |