CN106935839A - A kind of micro- cube of preparation method of composite of carbon coating potassium phosphotungstate - Google Patents
A kind of micro- cube of preparation method of composite of carbon coating potassium phosphotungstate Download PDFInfo
- Publication number
- CN106935839A CN106935839A CN201710341641.7A CN201710341641A CN106935839A CN 106935839 A CN106935839 A CN 106935839A CN 201710341641 A CN201710341641 A CN 201710341641A CN 106935839 A CN106935839 A CN 106935839A
- Authority
- CN
- China
- Prior art keywords
- cube
- micro
- potassium
- phosphotungstate
- preparation
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
-
- 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
-
- 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
Abstract
A kind of micro- cube of preparation method of composite of carbon coating potassium phosphotungstate; belong to chemical cell technical field; first prepare micro- cube of potassium phosphotungstate; again by potassium phosphotungstate micro- cube be dispersed in the mixed solution of ethanol and deionized water; add ammoniacal liquor, tetraethyl orthosilicate, resorcinol and formaldehyde; stirring reaction washs drying to after terminating, and dried solid powder is calcined under nitrogen protection；Solid powder after again will be calcined is etched in HF acid and removes silica, and centrifuging and taking solid phase is dried, and obtains micro- cube of composite of carbon coating potassium phosphotungstate.By the operation of simple preparation method and simplicity, micro- cube of size of the potassium phosphotungstate prepared is smaller, and pattern is homogeneous, advantageously accounts for the difficult problem of microstructure Lithium-ion embeding abjection.The composite that will be obtained on carbon parcel to micro- cube of potassium phosphotungstate is conductive higher, has preferable cyclic reversibility and stability and specific discharge capacity high in electrochemistry.
Description
Technical field
The invention belongs to chemical cell technical field, and in particular to micro- cube of composite of carbon coating potassium phosphotungstate makees lithium
The preparation method of ion battery positive electrode.
Background technology
Potassium phosphotungstate（K3PW12O40）It is heteropoly acid（Multi-metal oxygen cluster）One kind, potassium phosphotungstate is used as heteropoly acid point
More deep positive active material is studied in submanifold, due to its reversible polyelectron redox reaction causes that it has can
Reach 260Ah/kg specific capacities high（Its capacity is beyond commercialized common Li2CoO2The 150Ah/ of lithium ion battery
kg）And the excellent properties of fast charging and discharging.By XAFS (ray Absorption Fine Structures）Ray ripple studies heteropoly acid in oxidation
Electro transfer change in reduction process has drawn heteropoly acid molecule again in discharge process from [PMo (VI)12 O 40 ] 3- State
Obtain 24 electronics become [PMo ()12 O 40 ] 27- It is a key factor that heteropoly acid battery has height ratio capacity.Greatly
The characteristic of amount storage electronics also enables caesium phosphotungstate as the material of high-performance secondary cell.
However, being limited to lithium ion is difficult to electron transmission passage that is embedded and deviating from microstructure and Non-smooth surface, potassium phosphorus
Tungstates poorly conductive, directly affects application of the potassium phosphotungstate in lithium ion battery.
The content of the invention
It is an object of the invention to propose that a kind of preparation cost is cheap, equipment requirement is simple, the preferable carbon coating of electric conductivity
The preparation method that micro- cube of potassium phosphotungstate.
The present invention is comprised the following steps：
1）Prepare micro- cube of potassium phosphotungstate：
Reacted after potassium chloride solution is mixed with phosphotungstic acid aqueous solution, reaction is cooled to room temperature after terminating, separated to take
Solid phase, then scrubbed, drying are obtained, micro- cube of potassium phosphotungstate is obtained；
2）Prepare carbon coating micro- cube of composite of potassium phosphotungstate：
First by potassium phosphotungstate micro- cube be dispersed in the mixed solution of ethanol and deionized water, add ammoniacal liquor, positive silicic acid four
Ethyl ester, resorcinol and formaldehyde, stirring reaction wash drying to after terminating, and dried solid powder is forged under nitrogen protection
Burn；Solid powder after again will be calcined is etched 12 hours in HF acid, removes silica, and centrifuging and taking solid phase is dried, and obtains carbon
Cladding micro- cube of composite of potassium phosphotungstate.
Tetraethyl orthosilicate is hydrolyzed into silica as silicon source in the presence of ammoniacal liquor, and resorcinol and formaldehyde are in alkali
Resorcinol formaldehyde resin is generated under the conditions of property, resorcinol formaldehyde resin is in N2Lower 750 DEG C of calcinings are protected to obtain carbon, carbon can be with
Improve the electric conductivity of material.Silica does not work in micro- cube of composite of carbon coating potassium phosphotungstate, so using HF
Etch away, but HF will not destroy potassium phosphotungstic acid and carbon-coating.
The present invention is using the excellent electrochemical properties of potassium phosphotungstate --- one or more electronics of reversible gain and loss and protect
Hold that structure is constant, by the operation of simple preparation method and simplicity, micro- cube of size of the potassium phosphotungstate prepared is smaller, only
200~400nm, pattern is homogeneous, advantageously accounts for the difficult problem of microstructure Lithium-ion embeding abjection.By carbon parcel to potassium phosphorus tungsten
The composite obtained on micro- cube of hydrochlorate is conductive higher, has preferable cyclic reversibility and stability in electrochemistry
And specific discharge capacity high.
Micro- cube of carbon coating potassium phosphotungstate prepared by the inventive method（C@K3PW12O40）Size is smaller, and pattern is homogeneous, has
Beneficial to solving the problems, such as that the abjection of microstructure Lithium-ion embeding is difficult.In addition, K3PW12O40Micro- cube fully wrapped around in very thin
In carbon-coating, the structural stability that so make use of carbon excellent, electric conductivity, and more embedding lithium positions can be provided, so as to carry
The specific discharge capacity of the lithium ion battery with composite preparation high.Composite prepared by the present invention is used for lithium-ion electric
The positive electrode in pond, can improve the electric conductivity of heteropoly acid molecular cluster battery.
Further, step 1 of the present invention）In, potassium chloride and phosphorus tungsten in phosphotungstic acid aqueous solution in the potassium chloride solution
The mixing quality ratio of acid is 4: 3, and the potassium phosphotungstate size generated under this ratio is homogeneous, and surface is smooth.
Step 1 of the present invention）In, the concentration of the phosphotungstic acid aqueous solution is 2.3 × 10-3Mol/L, the potassium chloride solution
Concentration be 6.7 × 10-2mol/L.Micro- cube of potassium phosphotungstate is easily generated at this concentration, and pattern is homogeneous, surface is smooth,
Yield is higher.
It is fully contacted to be beneficial to potassium chloride and phosphotungstic acid, improves reaction rate, less accessory substance.Step 1）In, instead
It is 100 DEG C to answer temperature.
Step 2）In, the potassium phosphotungstate micro- cube of salt, ethanol, deionized water, ammoniacal liquor, tetraethyl orthosilicate, isophthalic
The rate of charge of diphenol and formalin is 300 mg: 85 ml: 20 ml: 1.2ml: 0.2 ml: 0.2 g: 0.3 ml.
The rate of charge of the ammoniacal liquor, tetraethyl orthosilicate, resorcinol and formalin is 1.2 ml: 0.2 ml: 0.2 g
∶0.3 ml；Using above rate of charge, ammoniacal liquor and tetraethyl orthosilicate react the silica to be formed and can be very good to wrap potassium
Micro- cube of phosphotungstate, ammoniacal liquor can excessively dissolve micro- cube of potassium phosphotungstate, and the amount of ammoniacal liquor is crossed at least will not be with positive silicic acid tetrem
Ester reaction is complete, and the amount of tetraethyl orthosilicate is excessive or very few all without the effect for reaching coated with silica.And, use with
Upper rate of charge, resorcinol and the reacted phenolic resin of formaldehyde can be wrapped in silicon dioxide layer well, and such as isophthalic two
The amount of phenol is crossed the product at most obtaining and is reunited seriously, and not exclusively, the amount of formaldehyde crossed and react at least not exclusively to cross carbon-coating parcel at least,
Cross and can at most make the excessive pollution environment of formalin residual in waste liquid.
Micro- cube of rate of charge of salt, ethanol and deionized water of the potassium phosphotungstate is 300 mg: 85 ml: 20 ml, this
The environment built under ratio is optimum response environment, and ethanol and deionized water can make silica best under this ratio
It is wrapped in above potassium phosphotungstic acid, the mg optimums of potassium phosphotungstic acid 300, because potassium phosphotungstic acid can excessively make part not wrap titanium dioxide
Silicon, I haven't seen you for ages excessively generates unnecessary silica spheres.
The ingredient proportion that it is critical only that each material of the above of materials synthesis, must be in strict accordance with above-mentioned ratio in building-up process
Example feeds intake.Because this ratio is obtained under a large amount of, experiment repeatedly, above-mentioned material is added or added less all can be to final material
Material is damaged.
In addition, the present invention is calcined 3 hours for 750 DEG C under nitrogen protection, temperature is too high to make carbon-coating damaged, and temperature is too low then
Carbon-coating electric conductivity is bad, and calcination time can also influence reaction, and the most suitable time through studying repeatedly, testing is 3 hours.
Percent by volume be 10% HF acid solutions be at present relatively be adapted to etching silicon dioxide acid solution.Use the method
The composite structure stabilization of generation, pattern is uniform, and covered effect is good, and electric conductivity is excellent.
Finally, the purpose of 60 DEG C of present invention vacuum drying is preferably to remove the moisture in composite, is so conducive to
The insertion of lithium ion, abjection when being made cell positive material discharge and recharge, increase specific discharge capacity and raising cycle performance.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of micro- cube of the potassium phosphotungstate prepared using the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of micro- cube of the carbon coating potassium phosphotungstate prepared using the present invention.
Fig. 3 is the transmission electron microscope picture of micro- cube of the carbon coating potassium phosphotungstate prepared using the present invention.
Fig. 4 is micro- cube of the potassium phosphotungstate prepared using the present invention and micro- cube of the carbon coating potassium phosphotungstate for preparing
X-ray diffractogram.
Fig. 5 is micro- cube of the filling as anode material for lithium-ion batteries of carbon coating potassium phosphotungstate prepared using the present invention
Discharge curve.
Specific embodiment
First, in order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments to this hair
It is bright to be described in detail.
Embodiment 1
1）Prepare micro- cube of potassium phosphotungstate：
800mg phosphotungstic acids are taken in 150ml beakers, adds 120mL water ultrasounds to be uniformly dissolved it, it is 2.3 × 10 to obtain concentration-3The phosphotungstic acid aqueous solution of mol/L.600mg potassium chloride is taken in 150mL beakers, adds 120mL water ultrasounds to be uniformly dissolved it,
It is 6.7 × 10 to obtain concentration-2The potassium chloride solution of mol/L.Phosphotungstic acid aqueous solution is put into the three hole flasks of 500mL,
100 DEG C are heated under oil bath, then obtained potassium chloride solution are added in the phosphotungstic acid aqueous solution at above-mentioned 100 DEG C,
The stirring reaction 1h at 100 DEG C, forms micro- cube of emulsion of potassium phosphotungstate, after reaction terminates, is cooled to room temperature, is centrifuged, and takes
Solid phase washing is separated, and is dried, and obtains micro- cube of potassium phosphotungstate.
2）Prepare micro- cube of the potassium phosphotungstate of carbon coating：
By step 1）Micro- cube of obtained potassium phosphotungstate takes out 300 mg and is dispersed in 85 ml ethanol and 20 ml deionizations
In the mixed solution of water, ammoniacal liquor, 0.2 ml tetraethyl orthosilicates, 0.2 g resorcinols and the 0.3 ml first of 1.2 ml are added
Aldehyde, stirs mixed solution 24 hours under normal temperature, it is fully reacted, and obtained sample is washed with deionized water and ethanol
Drying is washed, then sample is put into crucible, in tube furnace, calcined 3 hours for 750 DEG C under nitrogen protection.
Sample has just been entered 10% for preparing after cooling（Percent by volume）HF acid solutions in, etch 12 hours, purpose is removed
Silica is removed, centrifugation after having etched obtains solid phase and washed with deionized water and ethanol.Sample finally is put into vacuum to do
60 DEG C of dryings 12 hours in dry case, purpose removes excessive moisture, and micro- cube of carbon coating potassium phosphotungstate is just can obtain after drying.
Embodiment 2
1）Prepare micro- cube of potassium phosphotungstate：
800mg phosphotungstic acids are taken in 150ml beakers, adds 120mL water ultrasounds to be uniformly dissolved it, it is 2.3 × 10 to obtain concentration-3The phosphotungstic acid aqueous solution of mol/L.600mg potassium chloride is taken in 150mL beakers, adds 120mL water ultrasounds to be uniformly dissolved it,
It is 6.7 × 10 to obtain concentration-2The potassium chloride solution of mol/L.Phosphotungstic acid aqueous solution is put into the three hole flasks of 500mL,
100 DEG C are heated under oil bath, then obtained potassium chloride solution are added in the phosphotungstic acid aqueous solution at above-mentioned 100 DEG C,
1h is stirred at 100 DEG C, micro- cube of emulsion of potassium phosphotungstate is formed, after reaction terminates, room temperature is cooled to, is centrifuged, take solid phase
Washing is separated, and is dried, and obtains micro- cube of potassium phosphotungstate.
2）Prepare micro- cube of the potassium phosphotungstate of carbon coating：
By step 1）Micro- cube of obtained potassium phosphotungstate takes out 300 mg and is dispersed in 85 ml ethanol and 20 ml deionizations
In the mixed solution of water, ammoniacal liquor, 0.2 ml tetraethyl orthosilicates, 0.2 g resorcinols and the 0.3 ml first of 1.2 ml are added
Aldehyde, stirs mixed solution 24 hours under normal temperature, it is fully reacted, and obtained sample is washed with deionized water and ethanol
Drying is washed, then sample is put into crucible, in tube furnace, calcined 3 hours for 750 DEG C under nitrogen protection.
Sample has just been entered 10% for preparing after cooling（Percent by volume）HF acid solutions in, etch 12 hours, purpose is removed
Silica is removed, centrifugation after having etched obtains solid phase and washed with deionized water and ethanol.Sample finally is put into vacuum to do
60 DEG C of dryings 12 hours in dry case, purpose removes excessive moisture, and micro- cube of carbon coating potassium phosphotungstate is just can obtain after drying.
2nd, product checking：
As shown in figure 1, being the scanning electron microscope (SEM) photograph of micro- cube of the potassium phosphotungstate prepared using the inventive method.It can be seen that, it is prepared
Product be micro- cube of potassium phosphotungstate, size is smaller, and diameter is in 200~400nm or so.
As Fig. 2,3 are respectively the micro- cube of scanning of composite of carbon coating potassium phosphotungstate prepared using the inventive method
Electron microscope and transmission plot.It can be seen that, prepared product is micro- cube of composite of carbon coating potassium phosphotungstate, and diameter is left in 450nm
The right side, and it is left to be clearly visible that the Surface coating of micro- cube of potassium phosphotungstate one layer of about 30-40 nm according to transmission electron microscope picture
Right carbon-coating.
Fig. 4 be using the inventive method prepare micro- cube of composite of carbon coating potassium phosphotungstate, potassium phosphotungstate it is micro-
Cube X-ray powder diffraction figure.
Fig. 5 is micro- cube of the filling as anode material for lithium-ion batteries of carbon coating potassium phosphotungstate prepared using the present invention
Discharge curve.Under the testing current of 0.1mA, there is the Ah/kg of specific capacity 128 higher.And pure potassium phosphotungstic acid only has 77
Ah/kg, it is seen then that carbon coating is preferable to micro- cube of upper conductivity of composite material for preparing of potassium phosphotungstate, with specific volume higher
Amount.
Claims (8)
1. it is a kind of to prepare micro- cube of method of composite of carbon coating potassium phosphotungstate, it is characterised in that to comprise the following steps：
1）Reacted after potassium chloride solution is mixed with phosphotungstic acid aqueous solution, reaction is cooled to room temperature after terminating, separated
Solid phase, then scrubbed, drying are obtained, micro- cube of potassium phosphotungstate is obtained；
2）First by potassium phosphotungstate micro- cube be dispersed in the mixed solution of ethanol and deionized water, add ammoniacal liquor, positive silicic acid
Tetra-ethyl ester, resorcinol and formaldehyde, stirring reaction wash drying to after terminating, by dried solid powder under nitrogen protection
Calcining；Solid powder after again will be calcined is etched 12 hours in HF acid, removes silica, and centrifuging and taking solid phase is dried, obtained
Micro- cube of composite of carbon coating potassium phosphotungstate.
2. preparation method according to claim 1, it is characterised in that step 1）In, potassium chloride in the potassium chloride solution
It is 4: 3 with the mixing quality ratio of phosphotungstic acid in phosphotungstic acid aqueous solution.
3. preparation method according to claim 2, it is characterised in that the step 1）In, the potassium chloride solution it is dense
Spend is 6.7 × 10-2Mol/L, the concentration of the phosphotungstic acid aqueous solution is 2.3 × 10-3mol/L。
4. the preparation method according to claim 1 or 2 or 3, it is characterised in that step 1）In, the temperature conditionss of reaction are
100℃。
5. preparation method according to claim 1, it is characterised in that step 2）In, micro- cube of salt of the potassium phosphotungstate,
The rate of charge of ethanol, deionized water, ammoniacal liquor, tetraethyl orthosilicate, resorcinol and formalin is 300 mg: 85 ml: 20
ml∶1.2ml∶0.2 ml∶0.2 g∶0.3 ml。
6. preparation method according to claim 1, it is characterised in that step 2）In, the temperature conditionss of the calcining are 750
DEG C, the time is 3 hours.
7. preparation method according to claim 1, it is characterised in that step 2）In, the HF acid is concentration of volume percent
It is 10%.
8. preparation method according to claim 1, it is characterised in that step 2）In, the drying is 60 DEG C of vacuum drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710341641.7A CN106935839B (en) | 2017-05-16 | 2017-05-16 | A kind of preparation method of micro- cube of composite material of carbon coating potassium phosphotungstate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710341641.7A CN106935839B (en) | 2017-05-16 | 2017-05-16 | A kind of preparation method of micro- cube of composite material of carbon coating potassium phosphotungstate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106935839A true CN106935839A (en) | 2017-07-07 |
| CN106935839B CN106935839B (en) | 2019-06-14 |
Family
ID=59429690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710341641.7A Active CN106935839B (en) | 2017-05-16 | 2017-05-16 | A kind of preparation method of micro- cube of composite material of carbon coating potassium phosphotungstate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106935839B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110034287A (en) * | 2019-04-10 | 2019-07-19 | 扬州大学 | ZIF-67 coats potassium phosphomolybdate microballoon composite material and preparation method |
| CN111994956A (en) * | 2020-07-24 | 2020-11-27 | 扬州大学 | Titanium dioxide ball-coated potassium phosphotungstate composite material and preparation method and application thereof |
| CN113193184A (en) * | 2021-04-29 | 2021-07-30 | 扬州大学 | Preparation method of ZIF-67 coated potassium phosphotungstate composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985876A (en) * | 2014-05-15 | 2014-08-13 | 中国科学院化学研究所 | Method for performing in-situ controllable coating on lithium ion battery electrode material by phenolic resin |
| CN104638245A (en) * | 2015-02-13 | 2015-05-20 | 江苏科技大学 | Keggin type phosphomolybdate-graphene composite material for lithium ion battery and preparation method thereof |
| CN105217601A (en) * | 2015-11-05 | 2016-01-06 | 北京工业大学 | A kind of preparation method with the porous hollow carbon ball of high-specific surface area |
| CN105355858A (en) * | 2015-12-15 | 2016-02-24 | 扬州大学 | Method for preparing three-dimensional graphene coated cesium phosphotungstate microspheres |
| CN105958041A (en) * | 2016-07-18 | 2016-09-21 | 扬州大学 | Method for preparing hollow microporous carbon sphere coated nanometer sulfur molecular material |
-
2017
- 2017-05-16 CN CN201710341641.7A patent/CN106935839B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985876A (en) * | 2014-05-15 | 2014-08-13 | 中国科学院化学研究所 | Method for performing in-situ controllable coating on lithium ion battery electrode material by phenolic resin |
| CN104638245A (en) * | 2015-02-13 | 2015-05-20 | 江苏科技大学 | Keggin type phosphomolybdate-graphene composite material for lithium ion battery and preparation method thereof |
| CN105217601A (en) * | 2015-11-05 | 2016-01-06 | 北京工业大学 | A kind of preparation method with the porous hollow carbon ball of high-specific surface area |
| CN105355858A (en) * | 2015-12-15 | 2016-02-24 | 扬州大学 | Method for preparing three-dimensional graphene coated cesium phosphotungstate microspheres |
| CN105958041A (en) * | 2016-07-18 | 2016-09-21 | 扬州大学 | Method for preparing hollow microporous carbon sphere coated nanometer sulfur molecular material |
Non-Patent Citations (1)
| Title |
|---|
| XINRAN LI ET AL.: ""Facile synthesis and shape evolution of well-defined phosphotungstic acid potassium nanocrystals as a highly efficient visible-light-driven photocatalyst"", 《NANOSCALE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110034287A (en) * | 2019-04-10 | 2019-07-19 | 扬州大学 | ZIF-67 coats potassium phosphomolybdate microballoon composite material and preparation method |
| CN111994956A (en) * | 2020-07-24 | 2020-11-27 | 扬州大学 | Titanium dioxide ball-coated potassium phosphotungstate composite material and preparation method and application thereof |
| CN113193184A (en) * | 2021-04-29 | 2021-07-30 | 扬州大学 | Preparation method of ZIF-67 coated potassium phosphotungstate composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106935839B (en) | 2019-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104362311B (en) | Silicon-carbon composite microsphere anode material and preparation method thereof | |
| CN106450251B (en) | A kind of lithium ion battery negative material and preparation method thereof | |
| JP2022507401A (en) | Silicon-Carbon Composite Anode Material | |
| CN103441247B (en) | A kind of high performance silicon/graphene oxide negative material constructed based on chemical bond and preparation method thereof | |
| CN110492084B (en) | Spherical negative electrode composite material Si @ MXene with core-shell structure and preparation method thereof | |
| JP2015130340A (en) | Lithium nickel cobalt aluminum oxide composite positive electrode material, method for producing the same, and lithium ion secondary battery | |
| CN106892459A (en) | A kind of preparation method of micro- cube of potassium phosphotungstate | |
| CN104620427A (en) | Silicon-based composite and method for manufacturing same | |
| CN104505501B (en) | Negative electrode for lithium ion battery composite and preparation method thereof | |
| CN104617270B (en) | Preparation method of spherical hollow lithium titanate/graphene composite material as lithium battery negative material | |
| CN108565406A (en) | A kind of preparation method of lithium ion battery composite material and its combination electrode | |
| CN105161696B (en) | A kind of preparation method of graphene silicon nano composite material | |
| CN105655561B (en) | A kind of synthetic method of manganese phosphate lithium nanosheet | |
| CN105870430A (en) | Method for preparing three-dimensional graphene-phosphotungstate | |
| CN103931027A (en) | Porous complex, and method for preparing same | |
| CN102867947A (en) | Method for preparing carbon/silicon composite anode material based on oligomeric silsesquioxane | |
| CN106935839A (en) | A kind of micro- cube of preparation method of composite of carbon coating potassium phosphotungstate | |
| CN114031063B (en) | Sodium vanadium fluorophosphate nanocomposite and preparation method thereof | |
| Wang et al. | Construction of air-stable pre-lithiated SiOx anodes for next-generation high-energy-density lithium-ion batteries | |
| CN106410153A (en) | Titanium nitride-cladded nickel titanate composite material as well as preparation method and application thereof | |
| CN104393266A (en) | Silicon-carbon composite electrode material of core-shell structure and preparation method thereof | |
| CN109546101A (en) | The preparation method and lithium ion battery of nickel cobalt lithium aluminate cathode material | |
| CN105355858B (en) | A kind of method for preparing three-dimensional grapheme parcel caesium phosphotungstate microballoon | |
| CN108736001B (en) | Spherical porous silicon oxide negative electrode material and preparation method and application thereof | |
| CN109841826A (en) | A kind of preparation method and application of carbonaceous mesophase spherules/nano silicone composite sphere |
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 |