CN107910514A - A kind of preparation method of nitrogen-doped carbon cladding double-core shell titanium phosphate lithium or titanium phosphate sodium - Google Patents
A kind of preparation method of nitrogen-doped carbon cladding double-core shell titanium phosphate lithium or titanium phosphate sodium Download PDFInfo
- Publication number
- CN107910514A CN107910514A CN201711075235.7A CN201711075235A CN107910514A CN 107910514 A CN107910514 A CN 107910514A CN 201711075235 A CN201711075235 A CN 201711075235A CN 107910514 A CN107910514 A CN 107910514A
- Authority
- CN
- China
- Prior art keywords
- lithium
- titanium phosphate
- sodium
- carbon
- titanium
- 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.)
- Pending
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to the preparation method of a kind of nitrogen-doped carbon cladding double-core shell titanium phosphate lithium or titanium phosphate sodium, belongs to electrode material synthesis field.The preparation method is on the basis of primary conductive carbon and titanium phosphate lithium/titanium phosphate sodium are compound and carbon-coated for the first time, secondary uniform, fine and close cladding is realized in the process that solid particles surface oxidation polymerization is adhered to using dopamine, nitrogen-doped carbon cladding double-core shell titanium phosphate lithium or titanium phosphate sodium material are obtained after high temperature cabonization, efficiently solve the problems, such as titanium phosphate lithium and titanium phosphate sodium electronic conductivity is low and carbon coating layer is uneven, unsound, obtained titanium phosphate lithium and titanium phosphate sodium electrode performance are excellent, stablize.For the present invention using high yield, the titanium source of low cost, preparation method is simple, easy to operate, easy to utilize.
Description
Technical field
The present invention relates to the preparation method of a kind of nitrogen-doped carbon cladding double-core shell titanium phosphate lithium or titanium phosphate sodium, belong to water system
The preparation field of secondary battery cathode material.
Background technology
With scale energy storage and the popularization and application of electric vehicle engineering, performance to various chemical energy storage batteries it is also proposed that
Increasingly higher demands.Development scale energy storage technology need to primarily establish inexpensive, safe and environmental-friendly energy storage system.It is existing
Being able to widely studied chemical energy storage has lead-acid battery, nickel-cadmium cell, Ni-MH battery, flow battery and lithium ion battery etc..Its
Middle lithium ion battery energy density and energy conversion efficiency are high, and rated voltage is high, easy to form battery pack, is most widely closed
Note.But when being used for scale energy storage, easily trigger safety issue, limit application of the large-scale lithium ion battery in energy storage.Water
It is the research that lithium (sodium) ion battery electrode materials are mostly based on organic lithium ion and sodium-ion battery material, with reference to aqueous systems electricity
Solve liquid the characteristics of introduced and improved, have can water-filling system battery is easily produced, cost is low and the advantage of high security, into
For the energy storage device of new generation with development and application potentiality.
Water system lithium (sodium) ion battery cathode material of function admirable is one of key that battery performance ensures.Titanium phosphate lithium
It is suitable with titanium phosphate sodium electrode potential, and the crystal structure with NASICON types, ionic conductivity is good, has more on by phosphorus
Sour titanium lithium and titanium phosphate sodium are used for the report of water system lithium (sodium) ion battery anode.Usual this titanium-based phosphate material is adopted respectively
It is starting material with organic titanium sources such as the inorganic ti sources based on titanium dioxide and butyl titanates, passes through sol-gel, hydro-thermal method
With the mode batch mixing of mechanical ball mill mixing, then high-temperature calcination obtains in air and under inert atmosphere.Inorganic ti sources and organic titanium
Source is compared, and has the advantage that yield is high, cost is low, is more conducive to industrialization.There are process route mostly to answer for current preparation method
Miscellaneous, the problem of carbon coating is uneven low with electronic conductivity.Although as patent CN107068988A passed through with inorganic ti sources it is secondary
Carbon coating enables titanium phosphate lithium and titanium phosphate sodium electronic conductivity is low and the non-uniform problem of carbon coating effectively solves, but technique
Complexity, the method that two sections of carbon coatings all use spray drying, it is difficult to scale amplification production.106299267 A of CN also use nothing
Machine titanium source and secondary carbon-coated technique, but secondary carbon source carries out mechanical ball mill with first mixed presoma and mixes, it is difficult to accomplish uniformly
Carbon coating.Other patents are mostly there are complex technical process, and a carbon coating process, it is difficult to ensure titanium phosphate lithium and titanium phosphate
The uniformity and validity of the high electronic conductivity of sodium and carbon coating layer.
Poly-dopamine (PDA) material is the main active of the stickum of shell biology exocuticle secretion.DOPA
Amine autoxidation can polymerize in alkaline aqueous solution, and reaction condition is gentle, easily operated.It is super that correlative study finds that PDA has
Strong adhesive force, can not only form uniform clad on various matrixes (also including all kinds of nano materials), and can be into
One one-step functional, is such as grafted corresponding compound and prepares super hydrophilic or super-hydrophobic coating, graft phase answers functionalized polymer
Deng also having and poly-dopamine carbonization directly be prepared into the patent application of high specific surface area porous carbon.Therefore, PDA has extensive
Researching value and meaning.
The content of the invention
The purpose of the present invention is low for aqoue seconary battery negative material-titanium phosphate lithium and titanium phosphate sodium electronic conductivity
With the non-uniform problem of carbon coating, it is desirable to provide a kind of that there is commercial application prospect can guarantee that the excellent nitrogen of material property is mixed again
The preparation method of miscellaneous carbon coating double-core shell titanium phosphate lithium or titanium phosphate sodium.The present invention is based on the extremely strong spy of poly-dopamine adhesiveness
Point, use it for a carbon coating first has tentatively had the titanium phosphate lithium or titanium phosphate sodium of core shell structure, realizes titanium phosphate
The secondary uniform of lithium or titanium phosphate sodium coats, and nitrogen-doped carbon cladding double-core shell titanium phosphate lithium or titanium phosphate sodium are obtained after high temperature cabonization
Material.The titanium phosphate lithium and titanium phosphate sodium of the present invention significantly improves material because of compound and surface the preliminary cladding with a carbon source
Electronic conductivity inside material, and assign certain stability.On this basis, it is right using the extremely strong adhesiveness of poly-dopamine
Carbon coating, which is tentatively provided with the titanium phosphate lithium of core shell structure or the composite material of titanium phosphate sodium and carbon, realizes substantially uniformity
Attachment, the nitrogen-doped carbon cladding double-core shell titanium phosphate lithium or phosphoric acid that high temperature cabonization availability is stablized under inert atmosphere protection
Titanium sodium negative material.
The present invention solves the above problems the technical solution of use：Nitrogen-doped carbon coats double-core shell titanium phosphate lithium or titanium phosphate sodium
Preparation method, it is characterized in that the preparation method step is as follows：
(1) by lithium source or sodium source, titanium source, phosphorus source and doped chemical source by lithium, titanium, phosphorus, doped chemical molar ratio 0.95
~1.05: 1.9~2.1: 2.85~3.15: 0.01~0.1 is mixed, and obtains presoma；Lithium source is lithium hydroxide, di(2-ethylhexyl)phosphate
Hydrogen lithium, two lithium of phosphoric acid hydrogen, lithium oxalate, lithium acetate, lithium carbonate or lithium bicarbonate, sodium source is sodium hydroxide, sodium dihydrogen phosphate, phosphoric acid
One or more of disodium hydrogen, sodium oxalate, sodium acetate, sodium carbonate, sodium acid carbonate, titanium source is titanium dioxide, titanium hydroxide, inclined titanium
One or more of acid；Phosphorus source is phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate
One or more of；The doped metallic elements are aluminium, chromium, niobium, magnesium, vanadium, tin, bismuth, one or more of cadmium, doping metals
Element in the form of the hydroxide of inorganic salts and metallic element to add, and inorganic salts are carbonate, bicarbonate, nitrate, vinegar
Hydrochlorate or oxalates；Add a carbon source and dispersant, carbon source is glucose, sucrose, citric acid, acrylic acid, starch, dextrin,
Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, phenolic resin, furfural resin, epoxy resin, conductive carbon black, section's qin carbon
One or more of black, Super-p acetylene blacks, KS-6 graphite；Dispersant is water, methanol, ethanol, propyl alcohol, isopropanol, acetic acid second
Ester, glycol dimethyl ether, 1, one or more of 3 dioxolanes or tetrahydrofuran；It is 100% by the quality of presoma, carbon source
The quality of addition is 3~30%, dispersant add quality be 5%~50% on planetary ball mill with 200~500r/
Batch mixing is carried out when the rotating speed ball milling 1~12 of min is small, according to ball: batch mixing mass ratio adds ball for 5~10: 1；
(2) by the pulpous state presoma obtained by step 1, stirring and drying removes solvent, heating-up temperature in magnetic stirring apparatus is heated
For 40~900C, rotating speed is 50~600 revs/min；Then by obtained uniformly mixed powdery precursor in inert atmosphere protection
When constant temperature calcining 4~20 is small at a temperature of lower 5000C~10000C, the compound and preliminary carbon coating of a carbon is realized；
(3) according to ball: batch mixing mass ratio 5~10: 1 adds ball, the carbon coating product that step 2 is obtained is expert at
Ball mill grinding is carried out when small with the rotating speed ball milling 5~12 of 200~500r/min on planetary ball mill, obtained powder adds concentration
It is 8.5 in the Tris-HCl buffer solutions of 0.5~5g/L, to adjust pH, when stirring reaction 5~48 is small under room temperature 20-35 0C；DOPA
Amine obtains poly-dopamine layer in a carbon coating its surface auto polymerization, then, filters, is dried to obtain the presoma of powdery；
(4) by step 3 gained powdery precursor under inert atmosphere protection, the constant temperature at a temperature of the 0C of 500 0C~1000
When roasting 4~20 is small, second of nitrogen-doped carbon cladding is realized, obtain nitrogen-doped carbon cladding double-core shell titanium phosphate lithium/titanium phosphate sodium
Material.
Beneficial effects of the present invention：Using inorganic ti sources, by the compound and first carbon coating of a carbon, material ensure that
The electron conduction of itself；Then using the extremely strong adhesiveness of poly-dopamine, in room temperature and air atmosphere auto polymerization process and
High temperature cabonization realizes the carbon coating of N doping, effectively increases carbon coating effect, has extraordinary uniformity and very high
Compactness, and impart the N doping catalytic action of material, be obviously improved a carbon coating have core shell structure titanium phosphate lithium/
The specific capacity of titanium phosphate sodium plays and long circulating stability.The present invention uses inorganic ti sources, obtains high yield；Pass through mechanical ball
Presoma is made in mill batch mixing and stirring evaporative removal solvent, and realization uniformly cladding is dispersed with stirring in dopamine alkaline solution, makes system
Preparation Method is simple to operation, easy to industrialized production and application.
Brief description of the drawings
The SEM image of nitrogen-doped carbon cladding double-nucleocapsid structure titanium phosphate lithium prepared by Fig. 1 embodiments 1
The SEM image of the core shell structure titanium phosphate lithium of carbon coating twice prepared by Fig. 2 comparative examples
It is the battery that anode, LiMn2O4 are cathode under 1C that Fig. 3, which uses nitrogen-doped carbon cladding double-nucleocapsid structure titanium phosphate lithium,
Specific discharge capacity and coulombic efficiency with cycle-index change
- zero-curve is：Specific discharge capacity with cycle-index change；- △-curve is：Coulombic efficiency is with cycle-index
Change.
Left side ordinate：Specific discharge capacity, unit：mAh/g；Right side ordinate：Coulombic efficiency, unit：%；
Abscissa：Cycle-index.
Fig. 4 use twice carbon coating core shell structure titanium phosphate lithium discharge for the battery that anode, LiMn2O4 are cathode under 1C
Specific capacity and coulombic efficiency with cycle-index change
- ◇-curve is：Specific discharge capacity with cycle-index change；- zero-curve is：Coulombic efficiency is with cycle-index
Change.
Left side ordinate：Specific discharge capacity, unit：mAh/g；Right side ordinate：Coulombic efficiency, unit：%；
Abscissa：Cycle-index.
Embodiment
Below in conjunction with drawings and examples to a kind of preparation of nitrogen-doped carbon coated core-shell structure titanium phosphate lithium/titanium phosphate sodium
Method is described in further detail.
Embodiment 1
Lithium carbonate, titanium dioxide, ammonium dihydrogen phosphate are mixed to get presoma, make Li: Ti: P mole in presoma
Than for 1: 2: 3, glucose is added according to the 10% of presoma gross mass, then 30% according to presoma gross mass add go from
The mass ratio of sub- water progress ball milling, ball and batch mixing is 6: 1, and a slurry is taken out after ball milling 5h, and solvent is removed with stirring is dry
It is dried, heating-up temperature is 90 degree, then by obtained material in N2900 DEG C of perseverances are warming up to 5 DEG C/min under the atmosphere of gas
Warm 12h, realizes a carbon coating, obtains the product of a carbon coating core shell structure.Then, product is put into ball grinder, ball
The mass ratio of material is 6: 1, is taken out after ball milling 2h, is put into the 1g/L dopamines buffer solution (100mL) that pH value is 8.5, stirring
React 12 it is small when, obtain surface cladding poly-dopamine layer material, by obtained material in N2Protect lower 800 DEG C of constant temperature calcinings
4h, obtains nitrogen-doped carbon cladding double-nucleocapsid structure titanium phosphate lithium.
Test result：Electrode is prepared using the nitrogen-doped carbon coated core-shell structure titanium phosphate lithium of the present embodiment, and with excess
LiMn2O4Cathode is assembled into battery, with 5M LiNO3Aqueous solution is electrolyte, and under 1C multiplying powers, electrode discharge capacity is accomplished
117mAh/g, capacity retention ratio is 96% after circulating 500 weeks.
Embodiment 2
Sodium carbonate, titanium dioxide, diammonium hydrogen phosphate are mixed to get presoma, make Na: Ti: P mole in presoma
Than for 1: 2: 3, citric acid is added according to the 8% of presoma gross mass, then 30% according to presoma gross mass add go from
The mass ratio of sub- water progress ball milling, ball and batch mixing is 8: 1, and a slurry is taken out after ball milling 6h, and solvent is removed with stirring is dry
It is dried, heating-up temperature is 80 degree, then by obtained batch mixing in N2800 DEG C of perseverances are warming up to 5 DEG C/min under the atmosphere of gas
Warm 8h, realizes a carbon coating, obtains the product of a carbon coating core shell structure.Then, the mass ratio of ball and batch mixing is 6:
1, product is put into ball milling 2h in ball grinder, the powdery solid of taking-up is put into the 1.5g/L dopamine buffer solutions that pH value is 8.5
In (80mL), when stirring reaction 20 is small, the material of surface cladding poly-dopamine layer is obtained, by obtained material in N2Under protection
900 DEG C of constant temperature calcining 4h, obtain nitrogen-doped carbon cladding double-nucleocapsid structure titanium phosphate sodium.
Test result：Electrode is prepared using the nitrogen-doped carbon cladding double-nucleocapsid structure titanium phosphate sodium of the present embodiment, and with mistake
The activated carbon of amount is assembled into battery for cathode, with 5M LiNO3Aqueous solution is electrolyte, and under 1C multiplying powers, electrode discharge capacity is done
To 114mAh/g, capacity retention ratio is 97% after circulating 500 weeks.
Embodiment 3
Lithium carbonate, titanium dioxide, ammonium dihydrogen phosphate are mixed to get presoma, make Li: Ti: P mole in presoma
Than for 1: 2: 3, section's qin carbon black is added according to the 5% of presoma gross mass, then 20% according to presoma gross mass, which adds, goes
The mass ratio of ionized water progress ball milling, ball and batch mixing is 8: 1, and a slurry is taken out after ball milling 5h, is removed with agitating and heating molten
Agent is dried, and heating-up temperature is 70 degree, and the material for then obtaining evaporation drying is in N2Heated up under the atmosphere of gas with 5 DEG C/min
To 700 DEG C of constant temperature 12h, realize the compound of a carbon and titanium phosphate lithium, obtain the compound of conductive carbon and titanium phosphate lithium.Then,
Compound is put into ball grinder, the mass ratio of ball and batch mixing is 6: 1, is taken out after ball milling 2h, and it is 8.5 to be put into pH value
In 2g/L dopamines buffer solution (70mL), when stirring reaction 18 is small, the material of surface cladding poly-dopamine layer is obtained, will be obtained
Material in N2Lower 900 DEG C of constant temperature calcining 4h are protected, obtain nitrogen-doped carbon cladding double-nucleocapsid structure titanium phosphate lithium.
Test result：Electrode is prepared using the nitrogen-doped carbon cladding double-nucleocapsid structure titanium phosphate lithium of the present embodiment, and with mistake
The LiMn of amount2O4Cathode is assembled into battery, with 5M LiNO3Aqueous solution is electrolyte, and under 1C multiplying powers, electrode discharge capacity is accomplished
118mAh/g, capacity retention ratio is 98% after circulating 500 weeks.
Comparative example
Lithium carbonate, titanium dioxide, ammonium dihydrogen phosphate are mixed to get presoma, make Li: Ti: P mole in presoma
Than for 1: 2: 3, glucose is added according to the 10% of presoma gross mass, then 30% according to presoma gross mass add go from
The mass ratio of sub- water progress ball milling, ball and batch mixing is 8: 1, and a slurry is taken out after ball milling 5h, and solvent is removed with heating stirring
It is dried, heating-up temperature is 90 degree, and the material for then obtaining rotary evaporation is in N2It is warming up under the atmosphere of gas with 5 DEG C/min
700 DEG C of constant temperature 12h, realize the compound and preliminary carbon coating of a carbon and titanium phosphate lithium, obtain a carbon coating nucleocapsid knot
The compound of structure.Then, citric acid is added according to the gross mass 5% of a carbon coating product, by solid mixture gross mass
The mass ratio of 40% addition ethanol progress ball milling, ball and material is 6: 1, takes out secondary slurry after ball milling 5h, uses agitating and heating
Remove solvent to be dried, heating-up temperature is 90 degree, then by obtained material in N2It is warming up under the protection of gas with 5 DEG C/min
800 DEG C of constant temperature 4h, obtain carbon coating core shell structure titanium phosphate lithium twice.
Test result：Electrode is prepared using the core shell structure titanium phosphate lithium of carbon coating twice of the present embodiment, and with it is excessive
LiMn2O4Cathode is assembled into battery, with 5M LiNO3Aqueous solution is electrolyte, and under 1C multiplying powers, electrode discharge capacity is accomplished
90mAh/g, capacity retention ratio is only 50% after circulating 500 weeks.
Claims (1)
- A kind of 1. preparation method of nitrogen-doped carbon cladding double-core shell titanium phosphate lithium or titanium phosphate sodium, it is characterized in that the preparation method walks It is rapid as follows：(1) by lithium source or sodium source, titanium source, phosphorus source and doped chemical source by lithium, titanium, phosphorus, doped chemical molar ratio 0.95~ 1.05: 1.9~2.1: 2.85~3.15: 0.01~0.1 is mixed, and obtains presoma；Lithium source is lithium hydroxide, biphosphate Lithium, two lithium of phosphoric acid hydrogen, lithium oxalate, lithium acetate, lithium carbonate or lithium bicarbonate, sodium source is sodium hydroxide, sodium dihydrogen phosphate, phosphoric acid hydrogen One or more of disodium, sodium oxalate, sodium acetate, sodium carbonate, sodium acid carbonate, titanium source is titanium dioxide, titanium hydroxide, metatitanic acid One or more of；Phosphorus source is phosphoric acid, in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate More than one；The doped metallic elements are one or more of aluminium, chromium, niobium, magnesium, vanadium, tin, bismuth, cadmium, and doping metals are first Element in the form of the hydroxide of inorganic salts and metallic element to add, and inorganic salts are carbonate, bicarbonate, nitrate, acetic acid Salt or oxalates；A carbon source and dispersant are added, carbon source is glucose, sucrose, citric acid, acrylic acid, starch, dextrin, poly- Ethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, phenolic resin, furfural resin, epoxy resin, conductive carbon black, section's qin carbon black, One or more of Super-p acetylene blacks, KS-6 graphite；Dispersant for water, methanol, ethanol, propyl alcohol, isopropanol, ethyl acetate, Glycol dimethyl ether, 1, one or more of 3 dioxolanes or tetrahydrofuran；It is 100% by the quality of presoma, carbon source addition Quality be 3~30%, dispersant add quality be 5%~50% on planetary ball mill with 200~500r/min's Batch mixing is carried out when rotating speed ball milling 1~12 is small, according to ball: batch mixing mass ratio adds ball for 5~10: 1；(2) by the pulpous state presoma obtained by step 1, stirring and drying removes solvent, heating-up temperature 40 in magnetic stirring apparatus is heated ~90 DEG C, rotating speed is 50~600 revs/min；Then by obtained uniformly mixed powdery precursor 500 under inert atmosphere protection DEG C~1000 DEG C at a temperature of constant temperature calcining 4~20 it is small when, realize the compound and preliminary carbon coating of a carbon；(3) ball is added by ball material mass ratio 5~10: 1, the carbon coating product that step 2 is obtained is in planetary ball mill On it is small with the rotating speed ball milling 5~12 of 200~500r/min when carry out ball mill grinding, it is 0.5~5g/ that obtained powder, which adds concentration, In the Tris-HCl buffer solutions of L, it is 8.5 to adjust pH, when stirring reaction 5~48 is small at 20~35 DEG C of room temperature；Dopamine is in a carbon Cladding its surface auto polymerization obtains poly-dopamine layer, then, filters, is dried to obtain the presoma of powdery；(4) by step 3 gained powdery precursor under inert atmosphere protection, at a temperature of 500 DEG C~1000 DEG C constant temperature calcining 4~ 20 it is small when, realize second nitrogen-doped carbon cladding, obtain nitrogen-doped carbon cladding double-core shell titanium phosphate lithium/titanium phosphate sodium material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711075235.7A CN107910514A (en) | 2017-11-06 | 2017-11-06 | A kind of preparation method of nitrogen-doped carbon cladding double-core shell titanium phosphate lithium or titanium phosphate sodium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711075235.7A CN107910514A (en) | 2017-11-06 | 2017-11-06 | A kind of preparation method of nitrogen-doped carbon cladding double-core shell titanium phosphate lithium or titanium phosphate sodium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107910514A true CN107910514A (en) | 2018-04-13 |
Family
ID=61842721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711075235.7A Pending CN107910514A (en) | 2017-11-06 | 2017-11-06 | A kind of preparation method of nitrogen-doped carbon cladding double-core shell titanium phosphate lithium or titanium phosphate sodium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107910514A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109192520A (en) * | 2018-09-23 | 2019-01-11 | 齐鲁工业大学 | A kind of composite super capacitor based on waste and old zinc-maganese dioxide dry cell carbon packet |
| CN109346740A (en) * | 2018-09-23 | 2019-02-15 | 齐鲁工业大学 | The purposes of waste and old zinc-maganese dioxide dry cell carbon packet |
| CN111559741A (en) * | 2020-04-07 | 2020-08-21 | 哈尔滨工业大学 | Preparation method of polyanion composite material |
| CN113224307A (en) * | 2021-05-11 | 2021-08-06 | 陈双强 | Preparation method of high-capacity high-magnification high-voltage sodium vanadium fluorophosphate doped material |
| CN113697789A (en) * | 2021-08-27 | 2021-11-26 | 江苏理工学院 | Carbon-coated sodium titanium phosphate composite material and preparation method of negative electrode plate |
| CN113745486A (en) * | 2021-09-09 | 2021-12-03 | 中国石油大学(北京) | In-situ carbon-doped lithium titanium phosphate for water-based lithium ion battery and preparation method and application thereof |
| WO2021253714A1 (en) * | 2020-06-15 | 2021-12-23 | 宁波锋成先进能源材料研究院有限公司 | Carbon/titanium phosphate composite material and preparation method therefor and use thereof |
| CN114204030A (en) * | 2021-12-02 | 2022-03-18 | 南昌大学 | Modification method of lithium ferric manganese phosphate positive electrode material |
| CN114300659A (en) * | 2021-12-15 | 2022-04-08 | 山东精工电子科技有限公司 | Synthesis method and application of hard carbon-coated sodium ion battery nanocomposite |
| CN115064665A (en) * | 2022-04-29 | 2022-09-16 | 江苏理工学院 | Doped modified carbon-coated sodium titanium phosphate composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101807696A (en) * | 2010-04-12 | 2010-08-18 | 浙江大学 | Titanium phosphate lithium material used for cathode of lithium ion battery and preparation method thereof |
| CN104319424A (en) * | 2014-11-06 | 2015-01-28 | 中国科学技术大学 | Water-system sodium ion battery as well as manufacturing method and application thereof |
| CN106299267A (en) * | 2015-10-15 | 2017-01-04 | 肖水龙 | A kind of preparation method of titanium phosphate lithium titanate cathode material |
| CN106784696A (en) * | 2016-12-26 | 2017-05-31 | 深圳市贝特瑞纳米科技有限公司 | A kind of titanium phosphate sodium/carbon composite, Preparation Method And The Use |
-
2017
- 2017-11-06 CN CN201711075235.7A patent/CN107910514A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101807696A (en) * | 2010-04-12 | 2010-08-18 | 浙江大学 | Titanium phosphate lithium material used for cathode of lithium ion battery and preparation method thereof |
| CN104319424A (en) * | 2014-11-06 | 2015-01-28 | 中国科学技术大学 | Water-system sodium ion battery as well as manufacturing method and application thereof |
| CN106299267A (en) * | 2015-10-15 | 2017-01-04 | 肖水龙 | A kind of preparation method of titanium phosphate lithium titanate cathode material |
| CN106784696A (en) * | 2016-12-26 | 2017-05-31 | 深圳市贝特瑞纳米科技有限公司 | A kind of titanium phosphate sodium/carbon composite, Preparation Method And The Use |
Non-Patent Citations (2)
| Title |
|---|
| DAN SUN，XIA XUE等: "High-Rate LiTi2(PO4)3@N–C Composite via Bi-nitrogen Sources Doping", 《APPLIED MATERIALS & INTERFACES》 * |
| HONGSEN LI，LAIFA SHEN等: "Facile synthesis of N-doped carbon-coated Li4Ti5O12 microspheres using polydopamine as a carbon source for high rate lithium ion batteries", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109346740A (en) * | 2018-09-23 | 2019-02-15 | 齐鲁工业大学 | The purposes of waste and old zinc-maganese dioxide dry cell carbon packet |
| CN109346740B (en) * | 2018-09-23 | 2020-08-25 | 齐鲁工业大学 | Application of waste zinc-manganese dry battery carbon pack |
| CN109192520A (en) * | 2018-09-23 | 2019-01-11 | 齐鲁工业大学 | A kind of composite super capacitor based on waste and old zinc-maganese dioxide dry cell carbon packet |
| CN111559741A (en) * | 2020-04-07 | 2020-08-21 | 哈尔滨工业大学 | Preparation method of polyanion composite material |
| WO2021253714A1 (en) * | 2020-06-15 | 2021-12-23 | 宁波锋成先进能源材料研究院有限公司 | Carbon/titanium phosphate composite material and preparation method therefor and use thereof |
| CN113224307A (en) * | 2021-05-11 | 2021-08-06 | 陈双强 | Preparation method of high-capacity high-magnification high-voltage sodium vanadium fluorophosphate doped material |
| CN113697789A (en) * | 2021-08-27 | 2021-11-26 | 江苏理工学院 | Carbon-coated sodium titanium phosphate composite material and preparation method of negative electrode plate |
| CN113745486A (en) * | 2021-09-09 | 2021-12-03 | 中国石油大学(北京) | In-situ carbon-doped lithium titanium phosphate for water-based lithium ion battery and preparation method and application thereof |
| CN113745486B (en) * | 2021-09-09 | 2022-08-19 | 中国石油大学(北京) | In-situ carbon-doped lithium titanium phosphate for water-based lithium ion battery and preparation method and application thereof |
| CN114204030A (en) * | 2021-12-02 | 2022-03-18 | 南昌大学 | Modification method of lithium ferric manganese phosphate positive electrode material |
| CN114300659A (en) * | 2021-12-15 | 2022-04-08 | 山东精工电子科技有限公司 | Synthesis method and application of hard carbon-coated sodium ion battery nanocomposite |
| CN114300659B (en) * | 2021-12-15 | 2023-11-24 | 山东精工电子科技股份有限公司 | Method for synthesizing hard carbon coated sodium ion battery nanocomposite and application thereof |
| CN115064665A (en) * | 2022-04-29 | 2022-09-16 | 江苏理工学院 | Doped modified carbon-coated sodium titanium phosphate composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107910514A (en) | A kind of preparation method of nitrogen-doped carbon cladding double-core shell titanium phosphate lithium or titanium phosphate sodium | |
| US10957903B2 (en) | Layered lithium-rich manganese-based cathode material with olivine structured LIMPO4 surface modification and preparation method thereof | |
| WO2021253714A1 (en) | Carbon/titanium phosphate composite material and preparation method therefor and use thereof | |
| CN104603057B (en) | Carbon applies the preparation method of lithium iron phosphate nano powder | |
| CN104603060B (en) | The preparation method of lithium iron phosphate nano powder | |
| CN104918889B (en) | Method for preparing lithium iron phosphate nano powder | |
| CN110875473B (en) | Positive electrode active material, preparation method thereof and sodium ion battery | |
| CN110112388B (en) | Porous tungsten trioxide coated modified positive electrode material and preparation method thereof | |
| CN104577119A (en) | Cathode material LiMn1-xFexPO4 for lithium ion cell and preparation method of cathode material LiMn1-xFexPO4 | |
| CN108933237B (en) | Preparation method and application of lithium ion battery positive electrode material | |
| CN102427131A (en) | Preparation method for metal magnesium-doped lithium manganese phosphate/carbon cathode material of lithium ion battery | |
| CN106602038B (en) | A kind of hot method of colloidal sol secondary solvent prepares grain rod mixing pattern phosphoric acid vanadium lithium/carbon composite anode material and preparation method thereof | |
| CN107628594B (en) | Solvothermal preparation method of 3D flower-shaped lithium iron phosphate cathode material assembled by two-dimensional nanosheets | |
| CN104577123A (en) | Preparation method of cathode material for lithium ion cell | |
| CN103413944A (en) | Lithium manganese phosphate positive electrode material and preparation method thereof | |
| CN110790248B (en) | Iron-doped cobalt phosphide microsphere electrode material with flower-shaped structure and preparation method and application thereof | |
| CN101764217A (en) | Method for preparing nano-scale lithium iron phosphate | |
| CN103413918A (en) | Synthetic method for cathode material lithium cobaltous phosphate used for lithium ion batteries | |
| CN103378355B (en) | Alkali metal secondary battery and the preparation method of negative electrode active material, negative material, negative pole and negative electrode active material | |
| CN114057176A (en) | Lithium iron phosphate and preparation method and application thereof | |
| CN108736001A (en) | A kind of spherical porous silica negative material and its preparation method and application | |
| CN109449440B (en) | Microporous ultrathin soft carbon nanosheet and preparation method and application thereof | |
| CN107170976A (en) | A kind of preparation method of cobalt doped lithium titanate nano composite material | |
| CN102070199B (en) | Method for preparing micron frame-shaped manganese series lithium ion battery cathode material | |
| CN111916703A (en) | In-situ synthesis method of lithium iron manganese phosphate/carbon @ graphene composite material |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180413 |