CN105140489A - Titanium-doped carbon-coated sodium ferric phosphate material and preparation method thereof - Google Patents
Titanium-doped carbon-coated sodium ferric phosphate material and preparation method thereof Download PDFInfo
- Publication number
- CN105140489A CN105140489A CN201510617363.4A CN201510617363A CN105140489A CN 105140489 A CN105140489 A CN 105140489A CN 201510617363 A CN201510617363 A CN 201510617363A CN 105140489 A CN105140489 A CN 105140489A
- Authority
- CN
- China
- Prior art keywords
- doped carbon
- phosphoric acid
- titanium doped
- titanium
- acid ferrisodium
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/626—Metals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a titanium-doped carbon-coated sodium ferric phosphate material and a preparation method thereof. The titanium-doped carbon-coated sodium ferric phosphate material is prepared by virtue of the following method: taking cane sugar as a carbon source, taking ethanol as a dispersing agent, ball milling FeC2O4, NaH2PO4.2H2O, cane sugar and TiO2 in the ethanol, drying, re-milling, and calcining, to obtain the titanium-doped carbon-coated sodium ferric phosphate material. The particle size of primary particles of the titanium-doped carbon-coated sodium ferric phosphate material is 100nm to 300nm, the titanium-doped carbon-coated sodium ferric phosphate material has characteristics of short sodium ion dispersion distance, high transmission rate, high specific surface area, high conductivity, high ion transmission speed and the like, and is excellent in electrochemical performance, capable of being used as a positive material of a secondary sodium-ion battery, high in safety, cheap in price, wide in application range and applicable to an energy storage device, a backup power supply, a reserved power supply and the like. The preparation method is low in synthetic temperature, simple in procedures, easy for obtaining raw materials and convenient in industrialization.
Description
Technical field
The present invention relates to a kind of sodium-ion battery positive material and preparation method thereof, be specifically related to a kind of titanium doped carbon coated phosphoric acid ferrisodium material and preparation method thereof.
Background technology
From the nineties in 20th century, lithium ion battery, because having the advantages such as high-energy-density, quality be light, is now widely used in the electronic installations such as mobile device.But there is the defects such as price is high, reserves are limited in lithium ion battery.
CN102013496A discloses a kind of metallic titanium doped carbon-coating lithium iron phosphate and preparation method thereof, and its step is as follows: (1) is by lithium source, Fe
2o
3, TiO
2and NH
4h
2pO
4lithium in molar ratio: iron: titanium: the ratio of phosphorus=1:1-x:x:1 weighs prepares burden, wherein 0 < x≤0.2; (2) configured powder is added acetone to be placed on to rotate 2 ~ 10h under the speed of 200 ~ 500r/min in ball mill, the amount of acetone is 3 ~ 5 times of powder volume; (3) slurry in an oven at 100 ~ 110 DEG C after drying and grinding, the saturated aqueous solution adding citric acid afterwards makes the covert precursor of stream, and wherein the amount of citric acid is step (1) Raw lithium source, Fe by its phosphorus content
2o
3, TiO
2and NH
4h
2pO
420% of quality sum calculates; (4) by above-mentioned precursor under an inert atmosphere, heat up with the 1 DEG C/min rate of heat addition, in 100 DEG C of constant temperature 2 ~ 5h, then be warming up to 400 DEG C of constant temperature 3 ~ 6h, take out grinding with after stove cooling, under 100 ~ 200MPa pressure, be pressed into tight cylinder; (5) cylinder pressed is warming up to 500 ~ 900 DEG C of constant temperature calcining 5 ~ 15h under an inert atmosphere, is cooled to room temperature with stove and obtains the titanium doped carbon-covering lithium iron phosphate of anode material for lithium-ion batteries.Although the metallic titanium doped carbon-coating lithium iron phosphate of this method synthesis has higher specific discharge capacity, its cost is high, operating procedure is complicated, energy consumption is high.
Sodium-ion battery is lithium ion battery comparatively, and its cost of material is lower than lithium ion battery, and cell potential is higher than corresponding lithium ion battery current potential, and security performance is good.
The people such as AnnSun, FaithR.Beck (AnnSun, FaithR.Beck, etal.Synthesis, characterization, andelectrochemicalstudiesofchemicallysynthesizedNaFePO
4.materialsScienceandEngineering:B, Volume177, Issue20,1December2012, Pages1729-1733) with NaNO
3with Fe (NO
3)
29H
2o is raw material, adds citric acid and ethylene glycol, prepares NaFePO by sol-gel process
4presoma, at high temperature calcining obtains NaFePO
4material.Its concrete steps are as follows: the mol ratio of (1) metal ion total amount and citric acid and ethylene glycol is 1:0.5:0.5; (2) described sol gel reaction temperature is 60 DEG C, and the reaction time is 24h; (3) NaFePO
4presoma bake out temperature is 120 DEG C, and drying time is 24h; (4) described calcination atmosphere is inert atmosphere, and calcining heat is 550 ~ 600 DEG C.The NaFePO of this method synthesis
4though material cycle performance is higher, the capability retention after 30 times that circulates is that to enclose discharge capacity be 27.9mAhg to 138.1%(the 30th
-1), but discharge capacity is not high, and 0.1C first discharge capacity is 20.2mAhg
-1.
Summary of the invention
Technical problem to be solved by this invention is, overcome the above-mentioned defect that prior art exists, there is provided a kind of technique simple, be convenient to industrialization and control, product has high discharge capacity, titanium doped carbon coated phosphoric acid ferrisodium material of high rate cyclic superior performance and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is as follows: a kind of titanium doped carbon coated phosphoric acid ferrisodium material, is made up: take sucrose as carbon source, ethanol is dispersant, by FeC of following methods
2o
4, NaH
2pO
42H
2o, sucrose and TiO
2carry out ball milling in ethanol, through drying, returning mill, after calcining, obtaining titanium doped carbon coated phosphoric acid ferrisodium material.
Further, be specifically made up of following methods:
(1) by FeC
2o
4, NaH
2pO
42H
2o, sucrose and TiO
2be placed in ball grinder according to the ratio of mol ratio 0.8 ~ 1.0:1:0.18 ~ 0.28:0.01 ~ 0.2, then add ethanol, mix, ball milling, dry, obtain presoma;
(2) step (1) gained presoma is placed in ball mill to carry out returning mill, obtains Powdered presoma;
(3) the Powdered presoma of step (2) gained is calcined under an inert atmosphere, obtain titanium doped carbon coated phosphoric acid ferrisodium material.
In step (1), FeC
2o
4, NaH
2pO
42H
2o and TiO
2ratio be according to synthesized presoma NaFe
1-xti
xpO
4in (0.01≤x≤0.2) chemical formula, the mol ratio of each component is determined, each component addition too much or very few all can causing can not obtain target product or synthetic product poor-performing.
Further, in step (3), described calcining refers under an inert atmosphere, at 550 ~ 650 DEG C, and calcining 6 ~ 10h.The formation of final material is more conducive to, if the too high meeting of calcining heat causes material burning, if the too low meeting of calcining heat causes sintering insufficient under described calcination parameter condition.Due to glucose pyrogenetic decomposition under an inert atmosphere, make part carbon be coated on bulk material surface, being coated with of carbon is beneficial to the conductivity increasing material.
Further, in step (3), described calcining refers under an inert atmosphere, at 580 ~ 620 DEG C, and calcining 7 ~ 9h.
Further, in step (1), the ratio of described amount of alcohol added and material gross mass is 1 ~ 3:1.
Further, in step (1), the speed of described ball milling is 100 ~ 300r/min, and the time of ball milling is 3 ~ 7h.Described ball milling can make to be able to sufficient mechanical activation and dispersion between raw material, the milling intensity between the selection described raw material preferably of described ball milling speed and time conditions.
Further, in step (1), the speed of described ball milling is 150 ~ 250r/min, and the time of ball milling is 4 ~ 6h.
Further, in step (1), the temperature of described oven dry is 60 ~ 90 DEG C, and the time of oven dry is 10 ~ 24h.Oven dry can make material more easily carry out subsequent treatment, and whether described bake out temperature and time are according to the speed of drying materials and oxidizedly select.
Further, in step (2), described in return mill rotating speed be 100 ~ 200r/min, the time returning mill is 0.5 ~ 2h.Compare the ball milling of step (1), the rotating speed that step (2) returns mill is lower, time is shorter, returning mill can make material more even in follow-up sintering process, the selection returning abrasive stick part determines the impact of material pattern with returning to grind according to milling intensity, returning mill only need by non-Powdered presoma grinds powder, therefore time and rotating speed are all lower.
Further, in step (2), described in return mill rotating speed be 120 ~ 180r/min, the time returning mill is 0.8 ~ 1.5h.
Step (3) described inert atmosphere refers to that calcination process carries out under the protection such as high pure nitrogen, high-purity argon gas, high-purity gas purity >=99.99%.
The primary particle particle diameter of the carbon coated phosphoric acid ferrisodium material that the present invention is titanium doped is 100 ~ 300nm, has the characteristics such as sodium ion diffusion length is short, transmission rate fast, high-specific surface area, high conductivity, ion transfer are fast.Coated for titanium doped carbon phosphoric acid ferrisodium material is assembled into battery, and in 2.0 ~ 4.5V voltage range, under 1C multiplying power, first charge-discharge gram volume reaches as high as 63.7mAhg
-1; In charge and discharge process, have good cycle performance due to stable structure, 1C circulates after 50 times, and capability retention can reach 96.8%, and electrode and electrolyte side reaction reduce.Titanium doped carbon coated phosphoric acid ferrisodium material list has revealed excellent chemical property, and can be used as the positive electrode of secondary sodium-ion battery, fail safe is high, and low price is widely used, and can be applicable to energy storage device, back-up source, redundant electrical power etc.Preparation method's synthesis temperature of the present invention is low, and step is simple, and raw material is easy to get, and is convenient to industrialization.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the titanium doped carbon coated phosphoric acid ferrisodium material of the embodiment of the present invention 1 gained;
Fig. 2 is the SEM figure of the titanium doped carbon coated phosphoric acid ferrisodium material of the embodiment of the present invention 1 gained;
Fig. 3 is the EDX figure of the titanium doped carbon coated phosphoric acid ferrisodium material of the embodiment of the present invention 1 gained;
Fig. 4 is the 1C first charge-discharge curve chart of the titanium doped carbon coated phosphoric acid ferrisodium material of the embodiment of the present invention 1 gained;
Fig. 5 is 1C specific discharge capacity and the capability retention figure of the titanium doped carbon coated phosphoric acid ferrisodium material of the embodiment of the present invention 1 gained;
Fig. 6 is the 1C first charge-discharge curve chart of comparative example 1 gained carbon of the present invention coated phosphoric acid ferrisodium material.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
The embodiment of the present invention uses high-purity argon gas purity >=99.99%; The density of the ethanol used is 0.789g/mL; Other chemical reagent used, if no special instructions, is all obtained by routine business approach.
embodiment 1
(1) by 0.09mol(12.96g) FeC
2o
4, 0.1mol(15.6g) NaH
2pO
42H
2o, 0.022mol(7.53g) sucrose and 0.01mol(0.8g) TiO
2be placed in ball grinder, then add 60mL ethanol as dispersant, mix, with the rotating speed ball milling 4h of 200r/min, then in an oven, dry 15h with 80 DEG C, obtain presoma; (2) step (1) gained presoma is placed in ball mill, returns mill 1h with the rotating speed of 150r/min, obtain Powdered presoma; (3) by the Powdered presoma of step (2) gained under high-purity argon gas, at 600 DEG C, calcining 8h, obtain the coated NaFePO of titanium doped carbon
4material.
As shown in Figure 1, the titanium doped carbon coated phosphoric acid ferrisodium positive electrode degree of crystallinity of gained is high, and crystal formation is complete, and what detect is phosphoric acid ferrisodium.
As shown in Figure 2, the primary particle of the carbon coated phosphoric acid ferrisodium positive electrode that gained is titanium doped is comparatively homogeneous, and spherical in class, and particle diameter is 100 ~ 300nm.
As shown in Figure 3, titanium is effectively doped in the titanium doped carbon of gained coated phosphoric acid ferrisodium positive electrode.
Battery is assembled: take the NaFePO that 0.24g the present embodiment gained is titanium doped respectively
4material is as positive electrode, add 0.03g acetylene black (SP) and make conductive agent and 0.03gPVDF(HSV-900) make binding agent, 2mLNMP dispersion mixing is added after abundant grinding, slurry on 16 μm of thick aluminium foils of sizing mixing evenly makes anode pole piece, in anaerobism glove box with sodium metal sheet for negative pole, with WhatmanGF/D glass fibre for barrier film, 1mol/LNaClO
4/ EC:PC(volume ratio 1:1) be electrolyte, be assembled into the button cell of CR2025.
As shown in Figure 4, by battery in 2.0 ~ 4.5V voltage range, under 1C multiplying power, surveying its first charge-discharge gram volume is 63.7mAhg
-1.
As shown in Figure 5, by battery in 2.0 ~ 4.5V voltage range, under 1C multiplying power, circulate after 50 times, capability retention is 96.8%.
embodiment 2
(1) by 0.099mol(14.256g) FeC
2o
4, 0.1mol(15.6g) NaH
2pO
42H
2o, 0.019mol(6.5g) sucrose and 0.001mol(0.08g) TiO
2be placed in ball grinder, then add 120mL ethanol as dispersant, mix, with the rotating speed ball milling 3h of 100r/min, then in an oven, dry 10h with 60 DEG C, obtain presoma; (2) step (1) gained presoma is placed in ball mill, returns mill 0.5h with the rotating speed of 100r/min, obtain Powdered presoma; (3) by the Powdered presoma of step (2) gained under high-purity argon gas, at 550 DEG C, calcining 6h, obtain the coated NaFePO of titanium doped carbon
4material.
Battery is assembled: take the NaFePO that 0.24g the present embodiment gained is titanium doped respectively
4material is as positive electrode, add 0.03g acetylene black (SP) and make conductive agent and 0.03gPVDF(HSV-900) make binding agent, 2mLNMP dispersion mixing is added after abundant grinding, slurry on 16 μm of thick aluminium foils of sizing mixing evenly makes anode pole piece, in anaerobism glove box with sodium metal sheet for negative pole, with WhatmanGF/D glass fibre for barrier film, 1mol/LNaClO
4/ EC:PC(volume ratio 1:1) be electrolyte, be assembled into the button cell of CR2025, by battery in 2.0 ~ 4.5V voltage range, under 1C multiplying power, surveying its first charge-discharge gram volume is 51.9mAhg
-1.
embodiment 3
(1) by 0.08mol(11.52g) FeC
2o
4, 0.1mol(15.6g) NaH
2pO
42H
2o, 0.0263mol(9.0g) sucrose and 0.02mol(1.6g) TiO
2be placed in ball grinder, then add 90mL ethanol as dispersant, mix, with the rotating speed ball milling 7h of 300r/min, then in an oven, dry 24h with 90 DEG C, obtain presoma; (2) step (1) gained presoma is placed in ball mill, returns mill 2h with the rotating speed of 200r/min, obtain Powdered presoma; (3) by the Powdered presoma of step (2) gained under high-purity argon gas, at 650 DEG C, calcining 10h, obtain the coated NaFePO of titanium doped carbon
4material.
Battery is assembled: take the NaFePO that 0.24g the present embodiment gained is titanium doped respectively
4material is as positive electrode, add 0.03g acetylene black (SP) and make conductive agent and 0.03gPVDF(HSV-900) make binding agent, 2mLNMP dispersion mixing is added after abundant grinding, slurry on 16 μm of thick aluminium foils of sizing mixing evenly makes anode pole piece, in anaerobism glove box with sodium metal sheet for negative pole, with WhatmanGF/D glass fibre for barrier film, 1mol/LNaClO
4/ EC:PC(volume ratio 1:1) be electrolyte, be assembled into the button cell of CR2025, by battery in 2.0 ~ 4.5V voltage range, under 1C multiplying power, surveying its first charge-discharge gram volume is 58.7mAhg
-1.
comparative example 1
The difference of this comparative example technical scheme and embodiment 1 is only: in step (1), do not add TiO
2, finally obtain the coated NaFePO of carbon
4material.
Battery is assembled: take this comparative example of 0.24g gained NaFePO respectively
4material is as positive electrode, add 0.03g acetylene black (SP) and make conductive agent and 0.03gPVDF(HSV-900) make binding agent, 2mLNMP dispersion mixing is added after abundant grinding, slurry on 16 μm of thick aluminium foils of sizing mixing evenly makes anode pole piece, in anaerobism glove box with sodium metal sheet for negative pole, with WhatmanGF/D glass fibre for barrier film, 1mol/LNaClO
4/ EC:PC(volume ratio 1:1) be electrolyte, be assembled into the button cell of CR2025, by battery in 2.0 ~ 4.5V voltage range, under 1C multiplying power, surveying its first charge-discharge gram volume is 39.87mAhg
-1, as shown in Figure 6.Illustrate compared with comparative example 1, the doping of embodiment 1 titanium is more conducive to the chemical property improving battery.
Claims (10)
1. a titanium doped carbon coated phosphoric acid ferrisodium material, is characterized in that, be made up of following methods: take sucrose as carbon source, ethanol is dispersant, by FeC
2o
4, NaH
2pO
42H
2o, sucrose and TiO
2carry out ball milling in ethanol, through drying, returning mill, after calcining, obtaining titanium doped carbon coated phosphoric acid ferrisodium material.
2. carbon titanium doped according to claim 1 coated phosphoric acid ferrisodium material, is characterized in that, be specifically made up of following methods:
(1) by FeC
2o
4, NaH
2pO
42H
2o, sucrose and TiO
2be placed in ball grinder according to the ratio of mol ratio 0.8 ~ 1.0:1:0.18 ~ 0.28:0.01 ~ 0.2, then add ethanol, mix, ball milling, dry, obtain presoma;
(2) step (1) gained presoma is placed in ball mill to carry out returning mill, obtains Powdered presoma;
(3) the Powdered presoma of step (2) gained is calcined under an inert atmosphere, obtain titanium doped carbon coated phosphoric acid ferrisodium material.
3. carbon titanium doped according to claim 2 coated phosphoric acid ferrisodium material, is characterized in that: in step (3), described calcining refers under an inert atmosphere, at 550 ~ 650 DEG C, and calcining 6 ~ 10h.
4. carbon titanium doped according to Claims 2 or 3 coated phosphoric acid ferrisodium material, is characterized in that: in step (3), described calcining refers under an inert atmosphere, at 580 ~ 620 DEG C, and calcining 7 ~ 9h.
5., according to the described titanium doped carbon of one of claim 2 ~ 4 coated phosphoric acid ferrisodium material, it is characterized in that: in step (1), the ratio of described amount of alcohol added and material gross mass is 1 ~ 3:1.
6., according to the described titanium doped carbon of one of claim 2 ~ 5 coated phosphoric acid ferrisodium material, it is characterized in that: in step (1), the speed of described ball milling is 100 ~ 300r/min, and the time of ball milling is 3 ~ 7h.
7., according to the described titanium doped carbon of one of claim 2 ~ 6 coated phosphoric acid ferrisodium material, it is characterized in that: in step (1), the speed of described ball milling is 150 ~ 250r/min, and the time of ball milling is 4 ~ 6h.
8., according to the described titanium doped carbon of one of claim 2 ~ 7 coated phosphoric acid ferrisodium material, it is characterized in that: in step (1), the temperature of described oven dry is 60 ~ 90 DEG C, and the time of oven dry is 10 ~ 24h.
9., according to the described titanium doped carbon of one of claim 2 ~ 8 coated phosphoric acid ferrisodium material, it is characterized in that: in step (2), described in return mill rotating speed be 100 ~ 200r/min, the time returning mill is 0.5 ~ 2h.
10., according to the described titanium doped carbon of one of claim 2 ~ 9 coated phosphoric acid ferrisodium material, it is characterized in that: in step (2), described in return mill rotating speed be 120 ~ 180r/min, the time returning mill is 0.8 ~ 1.5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510617363.4A CN105140489B (en) | 2015-09-25 | 2015-09-25 | A kind of titanium doped carbon coating phosphoric acid ferrisodium material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510617363.4A CN105140489B (en) | 2015-09-25 | 2015-09-25 | A kind of titanium doped carbon coating phosphoric acid ferrisodium material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105140489A true CN105140489A (en) | 2015-12-09 |
| CN105140489B CN105140489B (en) | 2018-01-02 |
Family
ID=54725764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510617363.4A Active CN105140489B (en) | 2015-09-25 | 2015-09-25 | A kind of titanium doped carbon coating phosphoric acid ferrisodium material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105140489B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105845974A (en) * | 2016-06-06 | 2016-08-10 | 四川国润新材料有限公司 | Preparation method for positive electrode material NaFePO4/C of sodium ion battery |
| CN106684435A (en) * | 2016-12-27 | 2017-05-17 | 陕西科技大学 | Preparation method for NaFePO4/C nanosheet |
| CN108039491A (en) * | 2017-11-30 | 2018-05-15 | 华南理工大学 | A kind of anode material of lithium-ion battery triphosphoric acid ferrisodium and preparation method thereof |
| CN109449417A (en) * | 2018-11-01 | 2019-03-08 | 中科廊坊过程工程研究院 | A kind of phosphoric acid ferrisodium composite positive pole and its preparation method and application |
| CN111477872A (en) * | 2020-03-26 | 2020-07-31 | 合肥国轩电池材料有限公司 | Water-based lithium/sodium ion battery with iron-doped sodium titanium phosphate as negative electrode active material and preparation method thereof |
| CN114050250A (en) * | 2021-11-18 | 2022-02-15 | 中国科学技术大学 | Carbon-coated sodium iron phosphate sodium ion battery positive electrode material, and preparation method and application thereof |
| CN114050246A (en) * | 2021-11-16 | 2022-02-15 | 郑州大学 | Micron-sized porous sodium ferrous sulfate/carbon composite cathode material and sodium ion battery or sodium battery prepared from same |
| CN114068906A (en) * | 2021-10-15 | 2022-02-18 | 广东邦普循环科技有限公司 | Deposition type sodium iron phosphate cathode material and preparation method and application thereof |
| CN114759173A (en) * | 2022-03-21 | 2022-07-15 | 上海电力大学 | Trivalent chromium ion doped modified mixed ferric sodium pyrophosphate positive electrode material, preparation and application |
| CN114824205A (en) * | 2022-04-15 | 2022-07-29 | 宁波市稻禾科技有限公司 | Titanium-based fast ion conductor modified sodium iron phosphate positive electrode material, preparation method thereof and battery prepared from positive electrode material |
| CN115924878A (en) * | 2023-01-15 | 2023-04-07 | 西安交通大学 | Positive electrode material sodium iron phosphate for sodium ion battery and preparation method thereof |
| CN116750741A (en) * | 2023-05-29 | 2023-09-15 | 浙江鑫钠新材料科技有限公司 | Preparation method and application of titanium-doped carbon-coated sodium ferric pyrophosphate material |
| CN116779778A (en) * | 2023-08-11 | 2023-09-19 | 深圳海辰储能控制技术有限公司 | Positive electrode plate, preparation method thereof, energy storage device and power utilization device |
| CN118405680A (en) * | 2024-04-23 | 2024-07-30 | 兴荣新源(厦门)科技有限公司 | High-magnification sodium iron phosphate positive electrode material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372158C (en) * | 2001-04-06 | 2008-02-27 | 威伦斯技术公司 | Sodium ion batteries |
| US20080153002A1 (en) * | 2006-11-27 | 2008-06-26 | Nazar Linda Faye | Mixed Lithium/Sodium Ion Iron Fluorophosphate Cathodes for Lithium Ion Batteries |
| CN102668192A (en) * | 2009-12-24 | 2012-09-12 | 住友化学株式会社 | Electrode active material, electrode, and sodium secondary battery |
-
2015
- 2015-09-25 CN CN201510617363.4A patent/CN105140489B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372158C (en) * | 2001-04-06 | 2008-02-27 | 威伦斯技术公司 | Sodium ion batteries |
| US20080153002A1 (en) * | 2006-11-27 | 2008-06-26 | Nazar Linda Faye | Mixed Lithium/Sodium Ion Iron Fluorophosphate Cathodes for Lithium Ion Batteries |
| CN102668192A (en) * | 2009-12-24 | 2012-09-12 | 住友化学株式会社 | Electrode active material, electrode, and sodium secondary battery |
Non-Patent Citations (2)
| Title |
|---|
| JUN-CHAO ZHENG,ET AL.: ""Studies of Composite Cathode Material LiFePO4-Li3V2(PO4)3 and It’s Percursor FeVO4•xH2O"", 《BULLTIN OF THE CHEMICAL SOCIETY OF JAPAN》 * |
| SÉBASTIEN PATOUX ET AL.: ""Structural and Electrochemical Studies of Rhombohedral Na2TiM(PO4)3 and Li1.6Na0.4TiM(PO4)3 (M = Fe, Cr) Phosphates"", 《CHEM. MATER.》 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105845974A (en) * | 2016-06-06 | 2016-08-10 | 四川国润新材料有限公司 | Preparation method for positive electrode material NaFePO4/C of sodium ion battery |
| CN106684435A (en) * | 2016-12-27 | 2017-05-17 | 陕西科技大学 | Preparation method for NaFePO4/C nanosheet |
| CN106684435B (en) * | 2016-12-27 | 2019-03-05 | 陕西科技大学 | A kind of NaFePO4The preparation method of/C nano piece |
| CN108039491A (en) * | 2017-11-30 | 2018-05-15 | 华南理工大学 | A kind of anode material of lithium-ion battery triphosphoric acid ferrisodium and preparation method thereof |
| CN108039491B (en) * | 2017-11-30 | 2020-05-22 | 华南理工大学 | Sodium iron triphosphate as cathode material of sodium ion battery and preparation method thereof |
| CN109449417A (en) * | 2018-11-01 | 2019-03-08 | 中科廊坊过程工程研究院 | A kind of phosphoric acid ferrisodium composite positive pole and its preparation method and application |
| CN111477872A (en) * | 2020-03-26 | 2020-07-31 | 合肥国轩电池材料有限公司 | Water-based lithium/sodium ion battery with iron-doped sodium titanium phosphate as negative electrode active material and preparation method thereof |
| CN114068906A (en) * | 2021-10-15 | 2022-02-18 | 广东邦普循环科技有限公司 | Deposition type sodium iron phosphate cathode material and preparation method and application thereof |
| CN114050246A (en) * | 2021-11-16 | 2022-02-15 | 郑州大学 | Micron-sized porous sodium ferrous sulfate/carbon composite cathode material and sodium ion battery or sodium battery prepared from same |
| CN114050246B (en) * | 2021-11-16 | 2023-02-07 | 郑州大学 | Micron-sized porous sodium ferrous sulfate/carbon composite cathode material and sodium ion battery or sodium battery prepared from same |
| CN114050250A (en) * | 2021-11-18 | 2022-02-15 | 中国科学技术大学 | Carbon-coated sodium iron phosphate sodium ion battery positive electrode material, and preparation method and application thereof |
| CN114759173A (en) * | 2022-03-21 | 2022-07-15 | 上海电力大学 | Trivalent chromium ion doped modified mixed ferric sodium pyrophosphate positive electrode material, preparation and application |
| CN114824205A (en) * | 2022-04-15 | 2022-07-29 | 宁波市稻禾科技有限公司 | Titanium-based fast ion conductor modified sodium iron phosphate positive electrode material, preparation method thereof and battery prepared from positive electrode material |
| CN115924878A (en) * | 2023-01-15 | 2023-04-07 | 西安交通大学 | Positive electrode material sodium iron phosphate for sodium ion battery and preparation method thereof |
| CN116750741A (en) * | 2023-05-29 | 2023-09-15 | 浙江鑫钠新材料科技有限公司 | Preparation method and application of titanium-doped carbon-coated sodium ferric pyrophosphate material |
| CN116750741B (en) * | 2023-05-29 | 2024-09-06 | 浙江鑫钠新材料科技有限公司 | Preparation method and application of titanium-doped carbon-coated sodium ferric pyrophosphate material |
| CN116779778A (en) * | 2023-08-11 | 2023-09-19 | 深圳海辰储能控制技术有限公司 | Positive electrode plate, preparation method thereof, energy storage device and power utilization device |
| CN116779778B (en) * | 2023-08-11 | 2024-02-09 | 深圳海辰储能控制技术有限公司 | Positive electrode plate, preparation method thereof, energy storage device and power utilization device |
| CN118405680A (en) * | 2024-04-23 | 2024-07-30 | 兴荣新源(厦门)科技有限公司 | High-magnification sodium iron phosphate positive electrode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105140489B (en) | 2018-01-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105140489A (en) | Titanium-doped carbon-coated sodium ferric phosphate material and preparation method thereof | |
| Sandhya et al. | Lithium titanate as anode material for lithium-ion cells: a review | |
| CN102916179B (en) | Method for manufacturing industrialized high-energy lithium iron phosphate material | |
| Bi et al. | Recent advances in LiFePO 4 nanoparticles with different morphology for high-performance lithium-ion batteries | |
| CN103456936B (en) | Sodium ion secondary battery and the preparation method of layered titanate active substance, electrode material, both positive and negative polarity and active substance | |
| CN106876705B (en) | Preparation method of in-situ synthesized carbon/carbon nanotube coated lithium iron phosphate composite material | |
| Konarova et al. | Physical and electrochemical properties of LiFePO4 nanoparticles synthesized by a combination of spray pyrolysis with wet ball-milling | |
| CN105336924A (en) | Preparation method of carbon coated vanadium sodium phosphate positive electrode material | |
| CN103094550B (en) | Preparation method of lithium-rich anode material | |
| CN108155353B (en) | Graphitized carbon coated electrode material, preparation method thereof and application of graphitized carbon coated electrode material as energy storage device electrode material | |
| CN102509789A (en) | Method for preparing positive material fluorine-doped sodium vanadium phosphate of sodium-containing lithium ion battery | |
| CN105161688B (en) | A kind of phosphoric acid ferrisodium vanadium phosphate sodium composite of carbon coating and preparation method thereof | |
| CN101794876B (en) | Cathode material of battery with high rate performance and preparation method thereof | |
| CN102403505B (en) | Method for preparing in-situ carbon coated lithium manganese borate composite material by lithium ion battery cathode material | |
| CN103078113A (en) | Vanadium-titanium ion-codoped lithium iron phosphate material and preparation method thereof | |
| Lin et al. | One-step preparation of homogeneous single crystal Li-rich cathode materials with encouraging electrochemical performance | |
| CN103280579B (en) | High-performance lithium ion battery cathode material lithium ferric manganese phosphate and preparation method thereof | |
| CN103682292B (en) | The lithium titanate material preparation method of high-tap density | |
| CN105789606A (en) | Preparation method of lithium titanate coated lithium ion battery nickel cobalt manganese cathode material | |
| CN104852020A (en) | Lithium ion battery silicon oxide composite negative electrode material and preparation method thereof | |
| CN104201353A (en) | Titanium-series oxide/carbon nano tube composite anode material and preparation method thereof | |
| CN103050698A (en) | Vanadium lithium iron phosphate anode material and preparation method thereof | |
| CN102225753B (en) | Preparation method for lithium ion battery cathode materials | |
| CN114242980A (en) | Lithium iron phosphate composite material, preparation method and application | |
| CN103682276A (en) | Preparation method for cathode material LiVOPO4/C adopting sheet structure for lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |