CN105140489B - A kind of titanium doped carbon coating phosphoric acid ferrisodium material and preparation method thereof - Google Patents
A kind of titanium doped carbon coating phosphoric acid ferrisodium material and preparation method thereof Download PDFInfo
- Publication number
- CN105140489B CN105140489B CN201510617363.4A CN201510617363A CN105140489B CN 105140489 B CN105140489 B CN 105140489B CN 201510617363 A CN201510617363 A CN 201510617363A CN 105140489 B CN105140489 B CN 105140489B
- Authority
- CN
- China
- Prior art keywords
- phosphoric acid
- carbon coating
- doped carbon
- titanium doped
- 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.)
- Active
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
A kind of titanium doped carbon coating phosphoric acid ferrisodium material and preparation method thereof, the material is made up of following methods：Using sucrose as carbon source, ethanol is dispersant, by FeC2O4、NaH2PO4·2H2O, sucrose and TiO2Ball milling is carried out in ethanol, by drying, is returned mill, after calcining, is obtained titanium doped carbon coating phosphoric acid ferrisodium material.The primary particle particle diameter of the titanium doped carbon coating phosphoric acid ferrisodium material of the present invention is 100~300nm, with sodium ion diffusion length is short, transmission rate is fast, high-specific surface area, high conductivity, ion transmit the characteristic such as fast, show excellent chemical property, can be as the positive electrode of secondary sodium-ion battery, it is safe, it is cheap, it is widely used, can be applied to energy storage device, back-up source, redundant electrical power etc.；Preparation method synthesis temperature of the present invention is low, and step is simple, and raw material is easy to get, and is easy to industrialization.
Description
Technical field
The present invention relates to a kind of sodium-ion battery positive material and preparation method thereof, and in particular to a kind of titanium doped carbon bag
Cover phosphoric acid ferrisodium material and preparation method thereof.
Background technology
From in the 1990s, lithium ion battery has been widely used in because having the advantages that high-energy-density, light weight
The electronic installations such as mobile device.But there is the defects of price is high, reserves are limited in lithium ion battery.
The A of CN 102013496 disclose a kind of metallic titanium doped carbon-coating lithium iron phosphate and preparation method thereof, and its step is such as
Under：（1）By lithium source, Fe2O3、TiO2And NH4H2PO4Lithium in molar ratio:Iron:Titanium:Phosphorus=1:1-x:x:1 ratio, which weighs, to be carried out
Dispensing, wherein 0 ＜ x≤0.2；（2）It is placed in after the powder configured is added into acetone in ball mill with 200~500r/min speed
2~10h is rotated under rate, the amount of acetone is 3~5 times of powder volume；（3）In an oven at 100~110 DEG C after drying and grinding
The precursor of rheology phase is made in slurry, the saturated aqueous solution for adding citric acid afterwards, and the wherein amount of citric acid is by its phosphorus content
Step（1）Middle raw material lithium source, Fe2O3、TiO2And NH4H2PO4The 20% of quality sum calculates；（4）By above-mentioned precursor in indifferent gas
Under atmosphere, heated up with the 1 DEG C/min rates of heat addition, in 100 DEG C of 2~5h of constant temperature, then 400 DEG C of 3~6h of constant temperature are warming up to, after cooling with stove
Grinding is taken out, under 100~200MPa pressure, is pressed into close cylinder；（5）By the cylinder pressed under an inert atmosphere
500~900 DEG C of 5~15h of constant temperature calcining are warming up to, being cooled to room temperature with stove obtains that anode material for lithium-ion batteries is titanium doped to cover carbon
LiFePO4.Although the metallic titanium doped carbon-coating lithium iron phosphate of this method synthesis with higher specific discharge capacity, its cost is high,
Operating procedure is complicated, high energy consumption.
For sodium-ion battery is compared with lithium ion battery, its cost of material is lower than lithium ion battery, and cell potential is than corresponding
Lithium ion battery current potential is high, and has a safety feature.
Ann Sun, Faith R. Beck et al.（Ann Sun, Faith R. Beck, et al. Synthesis,
characterization, and electrochemical studies of chemically synthesized
NaFePO4. Materials Science and Engineering: B, Volume 177, Issue 20, 1
December 2012, Pages 1729-1733）With NaNO3With Fe (NO3)2·9H2O is raw material, adds citric acid and second
Allyl diglycol, NaFePO is prepared by sol-gel process4Presoma, at high temperature calcining obtain NaFePO4Material.It has
Body step is as follows：（1）Metal ion total amount is 1 with the mol ratio of citric acid and ethylene glycol:0.5:0.5；（2）It is described molten
Glue-gel reaction temperature is 60 DEG C, reaction time 24h；（3）NaFePO4Presoma drying temperature is 120 DEG C, drying time
For 24h；（4）The calcination atmosphere is inert atmosphere, and calcining heat is 550~600 DEG C.The NaFePO of this method synthesis4Though material
Cycle performance is higher, and capability retention is 138.1% after circulating 30 times（30th circle discharge capacity is 27.9 mAhg-1）, but put
Capacitance is not high, and discharge capacity is 20.2 mAhg to 0.1C first-1。
The content of the invention
The technical problems to be solved by the invention are to overcome drawbacks described above existing for prior art, there is provided a kind of technique letter
List, it is easy to industrialization control, product has high discharge capacity, the superior titanium doped carbon coating ferric phosphate of high-multiplying power discharge specific capacity
Sodium material 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 coating phosphoric acid ferrisodium material
Material, is made up of following methods：Using sucrose as carbon source, ethanol is dispersant, by FeC2O4、NaH2PO4·2H2O, sucrose and TiO2
Ball milling is carried out in ethanol, by drying, mill is returned, after calcining, obtains titanium doped carbon coating phosphoric acid ferrisodium material.
Further, specifically it is made up of following methods：
（1）By FeC2O4、NaH2PO4·2H2O, sucrose and TiO2According to mol ratio 0.8~1.0:1:0.18~0.28:
0.01~0.2 ratio is placed in ball grinder, adds ethanol, is well mixed, ball milling, drying, obtains presoma；
（2）By step（1）Gained presoma, which is placed in ball mill, to carry out returning mill, obtains powdered presoma；
（3）By step（2）The powdered presoma of gained is calcined under an inert atmosphere, obtains titanium doped carbon coating phosphoric acid ferrisodium
Material.
Step（1）In, FeC2O4、NaH2PO4·2H2O and TiO2Ratio be according to synthesized presoma NaFe1- xTixPO4（0.01≤x≤0.2）The mol ratio of each component determines in chemical formula, and each component addition is excessive or very few can
Cause that target product or synthetic product poor-performing can not be obtained.
Further, step（3）In, the calcining refers under an inert atmosphere, at 550~650 DEG C, calcines 6~10h.
The formation of final material is more beneficial under the conditions of the calcination parameter, if calcining heat is too high to cause material burning, if forging
Burn temperature it is too low can cause to sinter it is insufficient.Due to the pyrogenetic decomposition of glucose under an inert atmosphere so that part carbon bag
Overlay on bulk material surface, the electric conductivity being coated with beneficial to increase material of carbon.
Further, step（3）In, the calcining refers under an inert atmosphere, at 580~620 DEG C, calcines 7~9h.
Further, step（1）In, the ratio of the amount of alcohol added and material gross mass is 1~3:1.
Further, step（1）In, the speed of the ball milling is 100~300r/min, and the time of ball milling is 3~7h.It is described
Ball milling can make to be able to sufficient mechanical activation between raw material and disperse, and the selection of the ball milling speed and time conditions is preferably
Milling intensity between the raw material.
Further, step（1）In, the speed of the ball milling is 150~250r/min, and the time of ball milling is 4~6h.
Further, step（1）In, the temperature of the drying is 60~90 DEG C, and the time of drying is 10~24h.Drying can
Material is easier to make for subsequent treatment, the drying temperature and time be according to the speeds of drying materials and whether be oxidized come
Selection.
Further, step（2）In, the rotating speed for returning mill is 100~200r/min, and the time for returning mill is 0.5~2h.Phase
Compare step（1）Ball milling, step（2）Return that the rotating speed of mill is relatively low, and the time is shorter, return mill can make material during follow-up sintering more
Add uniformly, the selection for returning abrasive stick part is according to milling intensity and returns influence of the mill to material pattern and determine, return mill only need by
Non- powdered presoma is clayed into power shape, therefore time and rotating speed are all relatively low.
Further, step（2）In, the rotating speed for returning mill is 120~180r/min, and the time for returning mill is 0.8~1.5h.
Step（3）The inert atmosphere refers to that calcination process is carried out under the protection such as high pure nitrogen, high-purity argon gas, high-purity gas
Body purity >=99.99%.
The primary particle particle diameter of the titanium doped carbon coating phosphoric acid ferrisodium material of the present invention is 100~300nm, has sodium ion
The characteristics such as diffusion length is short, transmission rate is fast, the transmission of high-specific surface area, high conductivity, ion is fast.By titanium doped carbon coating phosphorus
Sour ferrisodium material is assembled into battery, and in 2.0~4.5V voltage ranges, under 1C multiplying powers, first charge-discharge gram volume reaches as high as
63.7mAh·g-1；In charge and discharge process, there is preferable cycle performance due to stable structure, after 1C is circulated 50 times, hold
Conservation rate is measured up to 96.8%, electrode is reduced with electrolyte side reaction.Titanium doped carbon coating phosphoric acid ferrisodium material shows excellent
Different chemical property, can be safe as the positive electrode of secondary sodium-ion battery, cheap, is widely used, can answer
For energy storage device, back-up source, redundant electrical power etc..Preparation method synthesis temperature of the present invention is low, and step is simple, and raw material is easy to get,
It is easy to industrialization.
Brief description of the drawings
Fig. 1 is the XRD of the titanium doped carbon coating phosphoric acid ferrisodium material of the gained of the embodiment of the present invention 1；
Fig. 2 is the SEM figures of the titanium doped carbon coating phosphoric acid ferrisodium material of the gained of the embodiment of the present invention 1；
Fig. 3 is the EDX figures of the titanium doped carbon coating phosphoric acid ferrisodium material of the gained of the embodiment of the present invention 1；
Fig. 4 is the 1C first charge-discharge curve maps of the titanium doped carbon coating phosphoric acid ferrisodium material of the gained of the embodiment of the present invention 1；
Fig. 5 is the 1C specific discharge capacities and capacity of the titanium doped carbon coating phosphoric acid ferrisodium material of the gained of the embodiment of the present invention 1
Conservation rate figure；
Fig. 6 is the 1C first charge-discharge curve maps of the gained carbon coating phosphoric acid ferrisodium material of comparative example 1 of the present invention.
Embodiment
With reference to 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 used ethanol is 0.789g/mL；
Chemical reagent used in other, unless otherwise specified, is obtained by routine business approach.
Embodiment 1
（1）By 0.09mol（12.96g）FeC2O4、0.1mol（15.6g）NaH2PO4·2H2O、0.022mol（7.53g）Sugarcane
Sugar and 0.01mol（0.8g）TiO2It is placed in ball grinder, adds 60mL ethanol as dispersant, be well mixed, with 200r/
Min rotating speed ball milling 4h, then in an oven, with 80 DEG C of drying 15h, obtain presoma；（2）By step（1）Gained presoma is put
In ball mill, mill 1h is returned with 150r/min rotating speed, obtains powdered presoma；（3）By step（2）The powdered presoma of gained
Under high-purity argon gas, at 600 DEG C, 8h is calcined, obtains titanium doped carbon coating NaFePO4Material.
As shown in figure 1, the carbon coating phosphoric acid ferrisodium positive electrode crystallinity height that gained is titanium doped, crystal formation is complete, detects
What is come is phosphoric acid ferrisodium.
As shown in Fig. 2 the primary particle of the titanium doped carbon coating phosphoric acid ferrisodium positive electrode of gained is more homogeneous, and it is in class
Spherical, particle diameter is 100~300nm.
As shown in figure 3, titanium is effectively doped in the titanium doped carbon coating phosphoric acid ferrisodium positive electrode of gained.
Battery assembles：NaFePO titanium doped obtained by 0.24g the present embodiment is weighed respectively4Material adds as positive electrode
Enter 0.03g acetylene blacks（SP）Make conductive agent and 0.03g PVDF（HSV-900）Make binding agent, 2mL NMP are added after being fully ground
Dispersion mixing, size mixing and anode pole piece uniformly is made after slurry on the aluminium foil of 16 μ m-thicks, with metallic sodium piece in anaerobism glove box
For negative pole, using Whatman GF/D glass fibres as barrier film, 1mol/L NaClO4/EC:PC（Volume ratio 1:1）For electrolyte, group
Dress up CR2025 button cell.
As shown in figure 4, by battery in 2.0~4.5V voltage ranges, under 1C multiplying powers, surveying its first charge-discharge gram volume is
63.7mAh·g-1。
As shown in figure 5, by battery in 2.0~4.5V voltage ranges, under 1C multiplying powers, after circulating 50 times, capability retention
For 96.8%.
Embodiment 2
（1）By 0.099mol（14.256g）FeC2O4、0.1mol（15.6g）NaH2PO4·2H2O、0.019mol（6.5g）
Sucrose and 0.001mol（0.08g）TiO2It is placed in ball grinder, adds 120mL ethanol as dispersant, is well mixed, with
100r/min rotating speed ball milling 3h, then in an oven, with 60 DEG C of drying 10h, obtain presoma；（2）By step（1）Gained forerunner
Body is placed in ball mill, is returned mill 0.5h with 100r/min rotating speed, is obtained powdered presoma；（3）By step（2）Gained is powdered
Presoma is under high-purity argon gas, at 550 DEG C, calcines 6h, obtains titanium doped carbon coating NaFePO4Material.
Battery assembles：NaFePO titanium doped obtained by 0.24g the present embodiment is weighed respectively4Material adds as positive electrode
Enter 0.03g acetylene blacks（SP）Make conductive agent and 0.03g PVDF（HSV-900）Make binding agent, 2mL NMP are added after being fully ground
Dispersion mixing, size mixing and anode pole piece uniformly is made after slurry on the aluminium foil of 16 μ m-thicks, with metallic sodium piece in anaerobism glove box
For negative pole, using Whatman GF/D glass fibres as barrier film, 1mol/L NaClO4/EC:PC（Volume ratio 1:1）For electrolyte, group
CR2025 button cell is dressed up, by battery in 2.0~4.5V voltage ranges, under 1C multiplying powers, surveys its first charge-discharge gram appearance
Measure as 51.9mAhg-1。
Embodiment 3
（1）By 0.08mol（11.52g）FeC2O4、0.1mol（15.6g）NaH2PO4·2H2O、0.0263mol（9.0g）Sugarcane
Sugar and 0.02mol（1.6g）TiO2It is placed in ball grinder, adds 90mL ethanol as dispersant, be well mixed, with 300r/
Min rotating speed ball milling 7h, then in an oven, with 90 DEG C of drying 24h, obtain presoma；（2）By step（1）Gained presoma is put
In ball mill, mill 2h is returned with 200r/min rotating speed, obtains powdered presoma；（3）By step（2）The powdered forerunner of gained
Body is under high-purity argon gas, at 650 DEG C, calcines 10h, obtains titanium doped carbon coating NaFePO4Material.
Battery assembles：NaFePO titanium doped obtained by 0.24g the present embodiment is weighed respectively4Material adds as positive electrode
Enter 0.03g acetylene blacks（SP）Make conductive agent and 0.03g PVDF（HSV-900）Make binding agent, 2mL NMP are added after being fully ground
Dispersion mixing, size mixing and anode pole piece uniformly is made after slurry on the aluminium foil of 16 μ m-thicks, with metallic sodium piece in anaerobism glove box
For negative pole, using Whatman GF/D glass fibres as barrier film, 1mol/L NaClO4/EC:PC（Volume ratio 1:1）For electrolyte, group
CR2025 button cell is dressed up, by battery in 2.0~4.5V voltage ranges, under 1C multiplying powers, surveys its first charge-discharge gram appearance
Measure as 58.7mAhg-1。
Comparative example 1
This comparative example technical scheme differs only in embodiment 1：Step（1）In, it is added without TiO2, finally obtain carbon bag
Cover NaFePO4Material.
Battery assembles：0.24g this comparative example gained NaFePO is weighed respectively4Material adds 0.03g second as positive electrode
Acetylene black（SP）Make conductive agent and 0.03g PVDF（HSV-900）Make binding agent, 2mL NMP dispersion mixings added after being fully ground,
Size mixing and anode pole piece uniformly is made after slurry on the aluminium foil of 16 μ m-thicks, using metallic sodium piece as negative pole in anaerobism glove box, with
Whatman GF/D glass fibres are barrier film, 1mol/L NaClO4/EC:PC（Volume ratio 1:1）For electrolyte, it is assembled into
CR2025 button cell, by battery in 2.0~4.5V voltage ranges, under 1C multiplying powers, surveying its first charge-discharge gram volume is
39.87mAh·g-1, as shown in Figure 6.Illustrate compared with comparative example 1, the doping of the titanium of embodiment 1 is more beneficial for improving the electricity of battery
Chemical property.
Claims (15)
1. a kind of titanium doped carbon coating phosphoric acid ferrisodium material, it is characterised in that be made up of following methods：
（1）By FeC2O4、NaH2PO4·2H2O, sucrose and TiO2According to mol ratio 0.8~1.0:1:0.18~0.28:0.01~
0.2 ratio is placed in ball grinder, adds ethanol, is well mixed, ball milling, drying, obtains presoma；
（2）By step（1）Gained presoma, which is placed in ball mill, to carry out returning mill, obtains powdered presoma；
（3）By step（2）The powdered presoma of gained under an inert atmosphere, at 580~620 DEG C, calcines 7~9h, obtains titanium and mix
Miscellaneous carbon coating phosphoric acid ferrisodium material.
2. titanium doped carbon coating phosphoric acid ferrisodium material according to claim 1, it is characterised in that：Step（1）In, the second
The ratio of alcohol addition and material gross mass is 1~3:1.
3. titanium doped carbon coating phosphoric acid ferrisodium material according to claim 1 or claim 2, it is characterised in that：Step（1）In, institute
The speed for stating ball milling is 100~300r/min, and the time of ball milling is 3~7h.
4. titanium doped carbon coating phosphoric acid ferrisodium material according to claim 1 or claim 2, it is characterised in that：Step（1）In, institute
The speed for stating ball milling is 150~250r/min, and the time of ball milling is 4~6h.
5. titanium doped carbon coating phosphoric acid ferrisodium material according to claim 1 or claim 2, it is characterised in that：Step（1）In, institute
The temperature for stating drying is 60~90 DEG C, and the time of drying is 10~24h.
6. titanium doped carbon coating phosphoric acid ferrisodium material according to claim 3, it is characterised in that：Step（1）In, the baking
Dry temperature is 60~90 DEG C, and the time of drying is 10~24h.
7. titanium doped carbon coating phosphoric acid ferrisodium material according to claim 4, it is characterised in that：Step（1）In, the baking
Dry temperature is 60~90 DEG C, and the time of drying is 10~24h.
8. titanium doped carbon coating phosphoric acid ferrisodium material according to claim 1 or claim 2, it is characterised in that：Step（2）In, institute
It is 100~200r/min to state and return the rotating speed of mill, and the time for returning mill is 0.5~2h.
9. titanium doped carbon coating phosphoric acid ferrisodium material according to claim 3, it is characterised in that：Step（2）In, it is described to return
The rotating speed of mill is 100~200r/min, and the time for returning mill is 0.5~2h.
10. titanium doped carbon coating phosphoric acid ferrisodium material according to claim 4, it is characterised in that：Step（2）In, it is described
The rotating speed for returning mill is 100~200r/min, and the time for returning mill is 0.5~2h.
11. titanium doped carbon coating phosphoric acid ferrisodium material according to claim 5, it is characterised in that：Step（2）In, it is described
The rotating speed for returning mill is 100~200r/min, and the time for returning mill is 0.5~2h.
12. titanium doped carbon coating phosphoric acid ferrisodium material according to claim 1 or claim 2, it is characterised in that：Step（2）In, institute
It is 120~180r/min to state and return the rotating speed of mill, and the time for returning mill is 0.8~1.5h.
13. titanium doped carbon coating phosphoric acid ferrisodium material according to claim 3, it is characterised in that：Step（2）In, it is described
The rotating speed for returning mill is 120~180r/min, and the time for returning mill is 0.8~1.5h.
14. titanium doped carbon coating phosphoric acid ferrisodium material according to claim 4, it is characterised in that：Step（2）In, it is described
The rotating speed for returning mill is 120~180r/min, and the time for returning mill is 0.8~1.5h.
15. titanium doped carbon coating phosphoric acid ferrisodium material according to claim 5, it is characterised in that：Step（2）In, it is described
The rotating speed for returning mill is 120~180r/min, and the time for 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 CN105140489A (en) | 2015-12-09 |
| CN105140489B true 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) |
Families Citing this family (13)
| 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 |
| CN106684435B (en) * | 2016-12-27 | 2019-03-05 | 陕西科技大学 | A kind of NaFePO4The preparation method of/C nano piece |
| 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 |
| CN109449417B (en) * | 2018-11-01 | 2021-11-16 | 中科廊坊过程工程研究院 | Sodium iron phosphate composite cathode material and preparation method and application thereof |
| 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 |
| CN114068906B (en) * | 2021-10-15 | 2023-07-07 | 广东邦普循环科技有限公司 | Deposition type sodium iron phosphate positive electrode material and preparation method and application thereof |
| 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 |
| CN114824205B (en) * | 2022-04-15 | 2022-11-29 | 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 |
| 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 |
Citations (1)
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080153002A1 (en) * | 2006-11-27 | 2008-06-26 | Nazar Linda Faye | Mixed Lithium/Sodium Ion Iron Fluorophosphate Cathodes for Lithium Ion Batteries |
| JP2011134551A (en) * | 2009-12-24 | 2011-07-07 | Sumitomo Chemical Co Ltd | Electrode active material, electrode, and sodium secondary battery |
-
2015
- 2015-09-25 CN CN201510617363.4A patent/CN105140489B/en active Active
Patent Citations (1)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105140489A (en) | 2015-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105140489B (en) | A kind of titanium doped carbon coating phosphoric acid ferrisodium material and preparation method thereof | |
| Mou et al. | Critical roles of semi-conductive LaFeO3 coating in enhancing cycling stability and rate capability of 5áV LiNi0. 5Mn1. 5O4 cathode materials | |
| CN103094550B (en) | Preparation method of lithium-rich anode material | |
| CN100448772C (en) | High density ultrafine composite ferric lithium phosphate anode material and preparation method | |
| CN106099098B (en) | High-voltage positive electrode material Li of lithium ion batteryδCo1-xMgxO2@AlF3And method for preparing the same | |
| CN105161688B (en) | A kind of phosphoric acid ferrisodium vanadium phosphate sodium composite of carbon coating and preparation method thereof | |
| CN105047924B (en) | A kind of lithium manganese silicate type positive electrode material of lithium ion battery and preparation method thereof | |
| CN103943854A (en) | Surface-coated modified lithium ion battery cathode material and preparation method thereof | |
| CN102082264B (en) | Method for preparing presoma of active electrode material of nano-lithium ion battery and application thereof | |
| CN103985871B (en) | The preparation method of LiFePO4 manganese cell positive electrode | |
| CN101308926B (en) | Lithium ionic cell composite positive pole material coated by orthosilicate and its preparation method | |
| CN102403505B (en) | Method for preparing in-situ carbon coated lithium manganese borate composite material by lithium ion battery cathode material | |
| CN104617293B (en) | A kind of preparation method of the carbon coated lithium ferrous phosphate composite material of fluorine richness | |
| CN105261744B (en) | A kind of preparation method of porous vanadium Mn oxide negative material | |
| CN102427131A (en) | Preparation method for metal magnesium-doped lithium manganese phosphate/carbon cathode material of lithium ion battery | |
| CN105226273B (en) | A kind of iron manganese phosphate for lithium and preparation method and application | |
| CN103280579B (en) | A kind of high performance lithium ion battery anode material lithium ferric manganese phosphate and preparation method thereof | |
| CN107482182A (en) | Carbon coating ion doping lithium manganese phosphate electrode material and preparation method thereof | |
| CN103078113A (en) | Vanadium-titanium ion-codoped lithium iron phosphate material and preparation method thereof | |
| CN101989653B (en) | Spherical anode materials for lithium ion batteries connected by ultramicro particles and preparation method thereof | |
| CN107910538A (en) | Graphene/carbon coats lithium manganese phosphate vanadium phosphate cathode material and preparation method | |
| CN105742592B (en) | A kind of carbon-coated method for preparing anode material of lithium-ion battery of W/W2C/ activity | |
| CN103682276A (en) | Preparation method for cathode material LiVOPO4/C adopting sheet structure for lithium ion battery | |
| CN107452950A (en) | The anode material for lithium-ion batteries and method of a kind of stable circulation | |
| Xin et al. | Conformal spinel/layered heterostructures of Co3O4 shells grown on single-crystal Li-rich nanoplates for high-performance lithium-ion batteries |
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 |