CN106299359A - A kind of carbon cladding vanadium phosphate cathode material and preparation method thereof - Google Patents
A kind of carbon cladding vanadium phosphate cathode material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to Material Field, relate to technical field of lithium ion, it is specifically related to a kind of carbon cladding vanadium phosphate cathode material and preparation method thereof, described method adds dehydrated alcohol after comprising the steps: to mix lithium source, vanadium source, phosphorus source and carbon source, it is placed in ball milling in ball grinder, being placed in the rotary furnace of three-temperature-zone sintering after drying, temperature is down to room temperature and i.e. be can get carbon cladding vanadium phosphate cathode material；Wherein, described carbon source is the mixed carbon source of sucrose and citric acid.The method that the present invention prepares carbon cladding vanadium phosphate cathode material is simple, it is possible to the anode material for lithium-ion batteries of preparation feather weight, possesses the electrical properties of excellence, is suitable for large-scale production.
Description
Technical field
The present invention relates to Material Field, relate to technical field of lithium ion, be specifically related to a kind of carbon cladding phosphoric acid vanadium lithium
Positive electrode and preparation method thereof.
Background technology
The research of electrokinetic cell and application, swift and violent in international and domestic development.Sony company in 1991 take the lead in releasing with
LiCoO2For the commercial lithium-ion batteries of positive electrode, LiCoO2Electrode material voltage stability, reversibility, discharge capacity,
The aspect function admirables such as efficiency for charge-discharge, and production technology is simple, is current most widely used lithium ion cell positive material
Material[1-6].But, along with people are higher for energy, the life-span is longer, the pursuit of the more preferable lithium ion battery of safety, existing
Industrialization LiCoO2Electrode material is difficult in extensive energy-storage battery and electrokinetic cell application.
As preferable anode material for lithium-ion batteries, it should have a performance of the following aspects: high potential, Fabrication of High Specific Capacitance
Amount, high stability and good cryogenic property, high rate performance and cycle performance etc..Meanwhile, from the point of view of prospects for commercial application, also
Require simple, the environmentally safe of raw material resources relative abundance, cheap and easy to get, preparation technology etc..
Traditional anode material for lithium-ion batteries is broadly divided into two big classes: a class is the transition metal oxysalt of lithium
LixMyOz, one or more during wherein M is usually the transition metal such as Co, Ni, Mn, V, Fe, or doping trace rare-earth element Sc,
Y, La, Ce, Nd etc.；Another kind of is containing tetrahedron or octahedral structure unit (XOm)n-Containing lithium polyanionic compound,
Wherein X is usually P, As, Si, Mo, V etc..
Cobalt acid lithium material has higher voltage, excellent cycle performance and high rate performance.But under overcharging state, positive pole
Upper unnecessary lithium ion still can move about to negative pole, forms lithium metal dendrite on negative pole, and dendrite is once formed, and just pierces through barrier film
Form the risk of internal short-circuit, the burning of carbonates electrolyte can be caused in the case of temperature is higher even to explode.Control
Being formed on low capacity lithium battery of Li dendrite is easier, and therefore cobalt acid lithium battery is currently limited to portable electric appts etc.
Small-capacity cells, the huge challenge in terms of electrokinetic cell then faces safety.Cobalt high cost simultaneously, and ambient pressure
Greatly.The advantage of LiMn2O4 is good rate capability, has high reversible capacity, high overcharging resisting ability, low cost, and toxicity is little, environment pressure
The features such as power is little.And manganese reserves relatively horn of plenty, preparation preparation technology is simple, and cost is relatively low.But owing to it is higher than 55 in temperature
DEG C time capacity attenuation fast especially, therefore high-temperature behavior and the cycle performance of LiMn2O4 are the best.
LiFePO4 has higher capacity, nontoxic, inexpensive, good heat stability, excellent charge-discharge performance
With the advantage such as high rate performance, consider from safety and battery cost angle, generally believe at present LiFePO4 be electrokinetic cell
Good novel anode material.But its electronic conductivity is low, lithium ion mobility speed is low, affect its extensively should as electrokinetic cell
With.Currently mainly by improving the preparation method of material and material is carried out Surface coating improving its chemical property.
Phosphoric acid vanadium lithium (the Li of monoclinic phase3V2(PO4)3) there are 3 lithium ion crystallography positions, can reversibly deintercalation.Tool
There are Stability Analysis of Structures, oxidation-reduction potential height, theoretical specific capacity high (being 197mAh/g when taking off lithium completely), heat stability and circulation
The advantages such as performance is good are it is considered to be a kind of great competitive advantage and the power lithium-ion battery positive electrode of application prospect.
CN 105655582 A discloses a kind of method using New Type of Carbon coating modification vanadium phosphate cathode material, described
Although positive electrode first discharge specific capacity prepared by method is big, but is also merely resting on laboratory stage, material in research process
Material preparation the most several grams to tens grams, assembling half-cell carries out positive electrode performance test.And the applied research of lithium battery needs
Assemble full battery, positive electrode large usage quantity, and along with material preparation amount increases, the uncertainty of its properties of product also increases.
Feather weight vanadium phosphate cathode material prepares rare report at present.
Summary of the invention
It is an object of the invention to provide a kind of carbon cladding vanadium phosphate cathode material and preparation method thereof, research and develop feather weight
The laboratory preparation techniques of cathode material lithium vanadium phosphate of lithium ion battery, is suitable to preparation and the popularization of industrialized production.
For reaching this goal of the invention, the present invention by the following technical solutions:
First aspect, the invention provides the preparation method of a kind of carbon cladding vanadium phosphate cathode material (LVP), its feature
It is, comprises the steps:
Add dehydrated alcohol after lithium source, vanadium source, phosphorus source and carbon source being mixed, be placed in ball milling in ball grinder, be placed in after drying
Sintering in the rotary furnace of three-temperature-zone, temperature is down to room temperature and i.e. be can get carbon cladding vanadium phosphate cathode material；
Wherein, described carbon source is the mixed carbon source of sucrose and citric acid.
In the present invention, use sucrose, citric acid as mixed carbon source, on the one hand utilize sucrose to provide enough carbon sources, another
Aspect utilizes citric acid catabolic process to take away part amorphous simple substance carbon with the form of carbon dioxide, reduces and is coated with LVP in material
The thickness of granule carbon-coating, promotes that cladding carbon-coating is uniformly distributed, contributes to carrying of the combination property such as material specific capacity, high rate performance
High.
Preferably, the frequency of described ball milling is 10-60Hz, can be such as 10Hz, 11Hz, 12Hz, 13Hz, 15Hz,
18Hz, 20Hz, 25Hz, 30Hz, 35Hz, 40Hz, 45Hz, 50Hz, 55Hz or 60Hz, preferably 15-35Hz, more preferably
25Hz。
Preferably, the time of described ball milling is 10-30h, can be such as 10h, 11h, 12h, 13h, 15h, 16h, 18h,
20h, 21h, 23h, 25h, 26h, 28h, 29h or 30h, preferably 12-20h, more preferably 16h.
Preferably, described dry temperature is 80-130 DEG C, can be such as 80 DEG C, 81 DEG C, 82 DEG C, 83 DEG C, 85 DEG C, 86
DEG C, 88 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C or 130 DEG C, preferably 90-110 DEG C,
More preferably 100 DEG C.
Preferably, described three-temperature-zone rotary furnace is sintered by temperature programmed control, described temperature programmed control particularly as follows: (1) room temperature extremely
300-400 DEG C, heating rate is 2-5 DEG C/min, and the time is 2-8h；(2) it is down to room temperature, grinds 10-60min；(3) room temperature is extremely
700-800 DEG C, heating rate is 2-5 DEG C/min, and the time is 10-20h, is down to room temperature.
Preferably, the temperature programmed control of described three-temperature-zone rotary furnace particularly as follows: (1) room temperature is to 350 DEG C, heating rate is 3 DEG C/
Min, the time is 5h；(2) it is down to room temperature, grinds 30min；(3) room temperature is to 750 DEG C, and heating rate is 3 DEG C/min, and the time is
16h, is down to room temperature.
Preferably, described in be sintered under inert gas shielding carrying out, described noble gas is in argon, helium or nitrogen
Any one or the mixing of at least two.
Preferably, described lithium source be in Lithium hydrate, lithium carbonate, lithium acetate, lithium fluoride or lithium oxalate any one or
The combination of at least two, preferably lithium carbonate.
Preferably, described vanadium source is vanadic anhydride and/or ammonium metavanadate, preferably vanadic anhydride.
Preferably, any one or at least two during phosphorus source is ammonium dihydrogen phosphate, diammonium phosphate or ammonium phosphate
Combination, preferably ammonium dihydrogen phosphate.
In the present invention, described lithium source: vanadium source: the amount of the material of phosphorus source is than for 3:2:3.
Preferably, the amount of the material of described carbon source carbon containing is (1-10) with the ratio of the amount of the material of phosphoric acid vanadium lithium: 1, such as
Can be preferably (2-6): 1, more preferably 3.6:1 with 1:1,2:1,3:1,4:1,5:1,6:1,7:1,8:1,9:1,10:1.
Preferably, described sucrose is 1:(0.2-5 with the ratio of the amount of the material of citric acid), such as can with 1:0.2,1:0.4,
1:0.5,1:0.8,1:1,1:2,1:3,1:4,1:5, preferably 1:(0.5-2), more preferably 1:1.
Preferably, a kind of carbon cladding vanadium phosphate cathode material preparation method, comprise the steps: by lithium carbonate, five
Adding dehydrated alcohol after V 2 O, ammonium dihydrogen phosphate and carbon source mixing, be placed in 25Hz ball milling 16h in ball grinder, 100 DEG C are dried
After, it being placed in the rotary furnace of three-temperature-zone sintering, be sintered under nitrogen gas protection carrying out, sintering process uses temperature programmed control, specifically
For (1) room temperature to 350 DEG C, heating rate is 3 DEG C/min, and the time is 5h；(2) it is down to room temperature, grinds 30min；(3) room temperature is extremely
750 DEG C, heating rate is 3 DEG C/min, and the time is 16h, and temperature is down to room temperature and i.e. be can get carbon cladding vanadium phosphate cathode material；
Wherein, described carbon source is the mixed carbon source of sucrose and citric acid, described phosphoric acid vanadium lithium and described carbon source phosphorus content
The ratio of the amount of material is 1:3.6, and the amount of the material of described sucrose and citric acid is than for 1:1；
Described lithium carbonate, vanadic anhydride, ammonium dihydrogen phosphate the amount of material than for 3:2:3.
Second aspect, the carbon that the present invention provides a kind of method as described in relation to the first aspect to prepare just is being coated with phosphoric acid vanadium lithium
Pole material.
Compared with prior art, the method have the advantages that
(1) present invention prepare carbon cladding vanadium phosphate cathode material method simple, it is possible to preparation feather weight lithium ion
Cell positive material, possesses the electrical properties of excellence, is suitable for large-scale production；
(2) the carbon cladding vanadium phosphate cathode material that prepared by the present invention, in 3.0-4.3V voltage range, discharge specific volume first
Amount 128.70mAh g-1, coulombic efficiency 99.6%, 100 specific discharge capacity 127.45mAh g-1, cycle efficieny 99.0%,
In 3.0-4.8V voltage range, discharge capacity 179.10mAh g first-1, 50 discharge capacity 150.05mAh g-1。
Accompanying drawing explanation
Fig. 1 is the flow chart that the embodiment of the present invention 1 prepares carbon cladding vanadium phosphate cathode material；
Fig. 2 is the XRD figure that the embodiment of the present invention 1 prepares carbon cladding vanadium phosphate cathode material.
Detailed description of the invention
Technical scheme is further illustrated below by detailed description of the invention.Those skilled in the art should be bright
, the only help of described embodiment understands the present invention, is not construed as the concrete restriction to the present invention.
Experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, the most commercially obtain.
Planetary ball mill, politef ball grinder Achates abrading-ball, PM4L type, speeds along the limited public affairs of development in science and technology in Nanjing
Department；
Test-type spray drying device, model MDR5, the Wuxi City modern times spray drying device company limited；
Three-temperature-zone rotary furnace, model OTF-1200X-5L-R-III, Hefei Ke Jing Materials Technology Ltd..
Embodiment 1
A kind of carbon cladding vanadium phosphate cathode material preparation method, its flow process as it is shown in figure 1, comprise the steps: by
Add dehydrated alcohol after lithium carbonate, vanadic anhydride, ammonium dihydrogen phosphate and carbon source mixing, be placed in 25Hz ball milling 16h in ball grinder,
100 DEG C dried, is placed in the rotary furnace of three-temperature-zone sintering, is sintered under nitrogen gas protection carrying out, and sintering process uses program
Temperature control, specially (1) room temperature is to 350 DEG C, and heating rate is 3 DEG C/min, and the time is 5h；(2) it is down to room temperature, grinds 30min；
(3) room temperature is to 750 DEG C, and heating rate is 3 DEG C/min, and the time is 16h, and temperature is down to room temperature and i.e. be can get carbon cladding phosphoric acid vanadium lithium
Positive electrode；
Wherein, described carbon source is the mixed carbon source of sucrose and citric acid, the material of phosphoric acid vanadium lithium and described carbon source carbon containing
The ratio of amount is 1:3.6, and the amount of the material of described sucrose and citric acid ratio is for 1:1.
The XRD figure of the carbon cladding vanadium phosphate cathode material of preparation is as in figure 2 it is shown, it can be seen that the crystalline substance of sample
It is mainly the Li of monocline mutually3V2(PO4)3Phase, belongs to P21/n space group, and each diffraction peak intensity height, narrowly distributing, degree of crystallinity are high.
Embodiment 2
The preparation method of a kind of carbon cladding vanadium phosphate cathode material, comprises the steps: lithium carbonate, five oxidations two
Adding dehydrated alcohol after vanadium, ammonium dihydrogen phosphate and carbon source mixing, be placed in 10Hz ball milling 30h in ball grinder, 80 DEG C dried, is placed in
Sintering in the rotary furnace of three-temperature-zone, be sintered under nitrogen gas protection carrying out, sintering process uses temperature programmed control, is specially (1) room
Temperature is to 300 DEG C, and heating rate is 2 DEG C/min, and the time is 8h；(2) it is down to room temperature, grinds 10min；(3) room temperature is to 700 DEG C, rises
Temperature speed is 2 DEG C/min, and the time is 10h, and temperature is down to room temperature and i.e. be can get carbon cladding vanadium phosphate cathode material；
Wherein, described carbon source is the mixed carbon source of sucrose and citric acid, the material of phosphoric acid vanadium lithium and described carbon source carbon containing
The ratio of amount is 1:5, and the amount of the material of described sucrose and citric acid ratio is for 1:1.
Embodiment 3
The preparation method of a kind of carbon cladding vanadium phosphate cathode material, comprises the steps: lithium carbonate, five oxidations two
Adding dehydrated alcohol after vanadium, ammonium dihydrogen phosphate and carbon source mixing, be placed in 60Hz ball milling 10h in ball grinder, 130 DEG C dried, puts
Sintering in the rotary furnace of three-temperature-zone, be sintered under nitrogen gas protection carrying out, sintering process uses temperature programmed control, is specially (1)
Room temperature is to 400 DEG C, and heating rate is 5 DEG C/min, and the time is 8h；(2) it is down to room temperature, grinds 60min；(3) room temperature is to 800 DEG C,
Heating rate is 5 DEG C/min, and the time is 20h, and temperature is down to room temperature and i.e. be can get carbon cladding vanadium phosphate cathode material；
Wherein, described carbon source is the mixed carbon source of sucrose and citric acid, the material of phosphoric acid vanadium lithium and described carbon source carbon containing
The ratio of amount is 1:5, and the amount of the material of described sucrose and citric acid ratio is for 1:2.
Embodiment 4
The preparation method of a kind of carbon cladding vanadium phosphate cathode material, comprises the steps: lithium carbonate, five oxidations two
Adding dehydrated alcohol after vanadium, ammonium dihydrogen phosphate and carbon source mixing, be placed in 50Hz ball milling 12h in ball grinder, 120 DEG C dried, puts
Sintering in the rotary furnace of three-temperature-zone, be sintered under nitrogen gas protection carrying out, sintering process uses temperature programmed control, is specially (1)
Room temperature is to 380 DEG C, and heating rate is 4 DEG C/min, and the time is 5h；(2) it is down to room temperature, grinds 40min；(3) room temperature is to 780 DEG C,
Heating rate is 4 DEG C/min, and the time is 16h, and temperature is down to room temperature and i.e. be can get carbon cladding vanadium phosphate cathode material；
Wherein, described carbon source is the mixed carbon source of sucrose and citric acid, the material of phosphoric acid vanadium lithium and described carbon source carbon containing
The ratio of amount is 1:3, and the amount of the material of described sucrose and citric acid ratio is for 1:0.5.
Embodiment 5
The preparation method of a kind of carbon cladding vanadium phosphate cathode material, comprises the steps: lithium carbonate, five oxidations two
Adding dehydrated alcohol after vanadium, ammonium dihydrogen phosphate and carbon source mixing, be placed in 80Hz ball milling 18h in ball grinder, 130 DEG C dried, puts
Sintering in the rotary furnace of three-temperature-zone, be sintered under nitrogen gas protection carrying out, sintering process uses temperature programmed control, is specially (1)
Room temperature is to 350 DEG C, and heating rate is 3 DEG C/min, and the time is 5h；(2) it is down to room temperature, grinds 30min；(3) room temperature is to 750 DEG C,
Heating rate is 3 DEG C/min, and the time is 16h, and temperature is down to room temperature and i.e. be can get carbon cladding vanadium phosphate cathode material；
Wherein, described carbon source is the mixed carbon source of sucrose and citric acid, the material of phosphoric acid vanadium lithium and described carbon source carbon containing
The ratio of amount is 1:3, and the amount of the material of described sucrose and citric acid ratio is for 1:3.
Comparative example 1
The preparation method of a kind of carbon cladding vanadium phosphate cathode material, comprises the steps: lithium carbonate, five oxidations two
Adding dehydrated alcohol after vanadium, ammonium dihydrogen phosphate and carbon source mixing, be placed in 25Hz ball milling 16h in ball grinder, 100 DEG C dried, puts
Sintering in the rotary furnace of three-temperature-zone, be sintered under nitrogen gas protection carrying out, sintering process uses temperature programmed control, is specially (1)
Room temperature is to 350 DEG C, and heating rate is 3 DEG C/min, and the time is 5h；(2) it is down to room temperature, grinds 30min；(3) room temperature is to 750 DEG C,
Heating rate is 3 DEG C/min, and the time is 16h, and temperature is down to room temperature and i.e. be can get carbon cladding vanadium phosphate cathode material；
Wherein, described carbon source is sucrose, and phosphoric acid vanadium lithium is 1:3.6 with the ratio of the amount of the material of described sucrose carbon containing；
Described lithium carbonate, vanadic anhydride, ammonium dihydrogen phosphate the amount of material than for 3:2:3.
Comparative example 2
The preparation method of a kind of carbon cladding vanadium phosphate cathode material, comprises the steps: lithium carbonate, five oxidations two
Adding dehydrated alcohol after vanadium, ammonium dihydrogen phosphate and carbon source mixing, be placed in 25Hz ball milling 16h in ball grinder, 100 DEG C dried, puts
Sintering in the rotary furnace of three-temperature-zone, be sintered under nitrogen gas protection carrying out, sintering process uses temperature programmed control, is specially (1)
Room temperature is to 350 DEG C, and heating rate is 3 DEG C/min, and the time is 5h；(2) it is down to room temperature, grinds 30min；(3) room temperature is to 750 DEG C,
Heating rate is 3 DEG C/min, and the time is 16h, and temperature is down to room temperature and i.e. be can get carbon cladding vanadium phosphate cathode material；
Wherein, described carbon source is citric acid, and phosphoric acid vanadium lithium is 1:3.6 with the ratio of the amount of the material of described citric acid carbon containing；
Described lithium carbonate, vanadic anhydride, ammonium dihydrogen phosphate the amount of material than for 3:2:3.
Comparative example 3
The preparation method of a kind of carbon cladding vanadium phosphate cathode material, comprises the steps: lithium carbonate, five oxidations two
Adding dehydrated alcohol after vanadium, ammonium dihydrogen phosphate and carbon source mixing, be placed in 25Hz ball milling 16h in ball grinder, 100 DEG C dried, puts
Sintering in the rotary furnace of three-temperature-zone, be sintered under nitrogen gas protection carrying out, sintering process uses temperature programmed control, is specially (1)
Room temperature is to 350 DEG C, and heating rate is 3 DEG C/min, and the time is 5h；(2) it is down to room temperature, grinds 30min；(3) room temperature is to 750 DEG C,
Heating rate is 3 DEG C/min, and the time is 16h, and temperature is down to room temperature and i.e. be can get carbon cladding vanadium phosphate cathode material；
Wherein, described carbon source is beta-schardinger dextrin-, and phosphoric acid vanadium lithium is 1 with the ratio of the amount of the material of described beta-schardinger dextrin-carbon containing:
3.6；
Described lithium carbonate, vanadic anhydride, ammonium dihydrogen phosphate the amount of material than for 3:2:3.
Performance test and sign:
The XRD figure of the carbon cladding vanadium phosphate cathode material of embodiment 1 preparation is as in figure 2 it is shown, LVP/C material is granule
Shape, Surface coating amorphous carbon layer, particle diameter is at about 300nm, and particle diameter distribution is more uniform, and the sample of synthesis has Li3V2(PO4)3
Principal phase, target material crystalline state is good.
The carbon cladding vanadium phosphate cathode material preparing embodiment 1-5 and comparative example 1-3 carries out electric performance test, test
Method is as follows:
Carbon is coated with vanadium phosphate cathode material, acetylene black, Kynoar by the quality proportioning of 82:10:8, addition one
Quantitative Solvents N-methyl-2-Pyrrolidone, puts into the mixed pulpous state of wearing into of agate mortar, and regulation is to certain viscosity, and slurry is equal
Even is applied on aluminium foil, and at 75 DEG C of dry 12h, makes NMP volatilize completely.Again with roll squeezer roll-in to reduce activity on thin slice
The porosity of material.Then slice stamping is become the electrode slice of required diameter (Coin Cell 2032, electrode slice Ф=14mm).
As positive pole, using metal lithium sheet as negative pole, microporous polypropylene membrane is as isolating membrane, with 1.0mol/L LiPF6/EC+DMC
The mixed solution of (1:1, mass ratio) is electrolyte.2032 type button cells it are assembled in the glove box of applying argon gas.With
Neware cell tester at room temperature carries out the conservation rate of capacity in battery capacity, cyclic process and the high rate performance of battery
Try Deng side.Discharge and recharge blanking voltage is 3.0-4.3V and 3.0-4.8V.
Test result is as shown in table 1:
Table 1
In sum, embodiment 1-5 finds out that carbon cladding vanadium phosphate cathode material, in 3.0-4.3V voltage range, is put first
Electricity specific capacity 125.4mAh g-1Above, coulombic efficiency more than 99.1%, 100 specific discharge capacity 124.42mAh g-1With
On, cycle efficieny more than 96.2%, in 3.0-4.8V voltage range, discharge capacity 175.2mAh g first-1Above, 50 times
Discharge capacity 146.21mAh g-1Above；Comparative example 1-3 is it can be seen that the carbon source that changes can affect carbon cladding phosphoric acid vanadium lithium positive pole
The combination property such as material specific capacity, cycle performance.
Applicant states, the present invention illustrates the process of the present invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned processing step, does not i.e. mean that the present invention has to rely on above-mentioned processing step and could implement.Art
Technical staff is it will be clearly understood that any improvement in the present invention, and equivalence to raw material selected by the present invention is replaced and auxiliary element
Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
1. the preparation method of a carbon cladding vanadium phosphate cathode material, it is characterised in that comprise the steps:
Add dehydrated alcohol after lithium source, vanadium source, phosphorus source and carbon source being mixed, be placed in ball milling in ball grinder, be placed in three temperature after drying
Sintering in district's rotary furnace, temperature is down to room temperature and i.e. be can get carbon cladding vanadium phosphate cathode material；
Wherein, described carbon source is the mixed carbon source of sucrose and citric acid.
Preparation method the most according to claim 1, it is characterised in that the frequency of described ball milling is 10-60Hz, is preferably
15-40Hz, more preferably 25Hz；
Preferably, the time of described ball milling is 10-30h, preferably 12-20h, more preferably 16h；
Preferably, described dry temperature is 80-130 DEG C, preferably 90-110 DEG C, more preferably 100 DEG C.
Preparation method the most according to claim 1 and 2, it is characterised in that described three-temperature-zone rotary furnace passes through temperature programmed control
Sintering, described temperature programmed control is particularly as follows: (1) room temperature is to 300-400 DEG C, and heating rate is 2-5 DEG C/min, and the time is 2-8h；(2)
It is down to room temperature, grinds 10-60min；(3) room temperature is to 700-800 DEG C, and heating rate is 2-5 DEG C/min, and the time is 10-20h, fall
To room temperature；
Preferably, the temperature programmed control of described three-temperature-zone rotary furnace is particularly as follows: (1) room temperature is to 350 DEG C, and heating rate is 3 DEG C/min,
Time is 5h；(2) it is down to room temperature, grinds 30min；(3) room temperature is to 750 DEG C, and heating rate is 3 DEG C/min, and the time is 16h, fall
To room temperature.
4. according to the preparation method according to any one of claim 1-3, it is characterised in that described in be sintered in inert gas shielding
Under carry out, described noble gas is any one or the mixing of at least two in argon, helium or nitrogen.
5. according to the method according to any one of claim 1-4, it is characterised in that described lithium source be Lithium hydrate, lithium carbonate,
Any one or the combination of at least two, preferably lithium carbonate in lithium acetate, lithium fluoride or lithium oxalate.
6. according to the method according to any one of claim 1-5, it is characterised in that described vanadium source be vanadic anhydride and/or
Ammonium metavanadate, preferably vanadic anhydride.
7. according to the method according to any one of claim 1-6, it is characterised in that phosphorus source is ammonium dihydrogen phosphate, phosphoric acid
Any one or the combination of at least two, preferably ammonium dihydrogen phosphate in hydrogen diammonium or ammonium phosphate.
8. according to the method according to any one of claim 1-7, it is characterised in that the amount of the material of described carbon source carbon containing and phosphorus
The ratio of the amount of the material of acid vanadium lithium is (1-10): 1, is preferably (2-6): 1, more preferably 3.6:1；
Preferably, described sucrose is 1:(0.2-5 with the ratio of the amount of the material of citric acid), preferably 1:(0.5-2), the most excellent
Elect 1:1 as.
9. according to the method according to any one of claim 1-8, it is characterised in that comprise the steps:
Add dehydrated alcohol after lithium carbonate, vanadic anhydride, ammonium dihydrogen phosphate and carbon source being mixed, be placed in 25Hz ball in ball grinder
Mill 16h, 100 DEG C dried, is placed in the rotary furnace of three-temperature-zone sintering, is sintered under nitrogen gas protection carrying out, and sintering process is adopted
With temperature programmed control, specially (1) room temperature is to 350 DEG C, and heating rate is 3 DEG C/min, and the time is 5h；(2) it is down to room temperature, grinds
30min；(3) room temperature is to 750 DEG C, and heating rate is 3 DEG C/min, and the time is 16h, and temperature is down to room temperature and i.e. be can get carbon cladding phosphorus
Acid vanadium lithium anode material；
Wherein, described carbon source is the mixed carbon source of sucrose and citric acid, the amount of the material of described phosphoric acid vanadium lithium and carbon source carbon containing
Than being 1:3.6, the amount of the material of described sucrose and citric acid ratio is for 1:1；
Described lithium carbonate, vanadic anhydride, ammonium dihydrogen phosphate the amount of material than for 3:2:3.
10. the carbon cladding vanadium phosphate cathode material that a method as claimed in any one of claims 1-9 wherein prepares.
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Citations (5)
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| CN101304084A (en) * | 2007-05-11 | 2008-11-12 | 深圳市比克电池有限公司 | Method for preparing Li3V2(PO4)3/C composite anode material and anode material made by the same |
| CN101889361A (en) * | 2007-12-11 | 2010-11-17 | 威伦斯技术公司 | Process for producing electrode active material for lithium ion cell |
| CN102394302A (en) * | 2011-12-09 | 2012-03-28 | 东莞市迈科科技有限公司 | Preparation method of lithium ion battery cathode material of vanadium lithium phosphate |
| JP2013077377A (en) * | 2011-09-29 | 2013-04-25 | Fuji Heavy Ind Ltd | Modified phosphoric acid vanadium lithium carbon complex, method of manufacturing the same, lithium secondary battery positive electrode active material and lithium secondary battery |
| CN104779393A (en) * | 2015-04-15 | 2015-07-15 | 河北民族师范学院 | Method for preparing lithium-vanadium-phosphate lithium ion battery positive material by means of liquid phase reduction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101304084A (en) * | 2007-05-11 | 2008-11-12 | 深圳市比克电池有限公司 | Method for preparing Li3V2(PO4)3/C composite anode material and anode material made by the same |
| CN101889361A (en) * | 2007-12-11 | 2010-11-17 | 威伦斯技术公司 | Process for producing electrode active material for lithium ion cell |
| JP2013077377A (en) * | 2011-09-29 | 2013-04-25 | Fuji Heavy Ind Ltd | Modified phosphoric acid vanadium lithium carbon complex, method of manufacturing the same, lithium secondary battery positive electrode active material and lithium secondary battery |
| CN102394302A (en) * | 2011-12-09 | 2012-03-28 | 东莞市迈科科技有限公司 | Preparation method of lithium ion battery cathode material of vanadium lithium phosphate |
| CN104779393A (en) * | 2015-04-15 | 2015-07-15 | 河北民族师范学院 | Method for preparing lithium-vanadium-phosphate lithium ion battery positive material by means of liquid phase reduction |
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