CN106328911B - Anion and cation doped carbon-coated sodium vanadium phosphate cathode material and preparation method thereof - Google Patents
Anion and cation doped carbon-coated sodium vanadium phosphate cathode material and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种阴阳离子掺杂碳包覆磷酸钒钠正极材料及其制备方法，其特征在于：磷酸钒钠正极材料的通式为Na3V2‑xMx(PO4‑y)3Y3y/C，其中0＜x≤0.2，0＜y≤0.05，M为Al、Fe、Cr、Ni、Co、Mg、Zn、La、Cu、Mn、Ti、Mo、Sn、Sr、Nb、Ce或Y，Y为F或Cl。本发明通过对磷酸钒钠正极材料进行碳包覆和阴阳离子共掺杂改性，提升了材料的电子电导率，并使材料的电化学性能显著提高。The invention discloses an anion and cation doped carbon-coated sodium vanadium phosphate positive electrode material and a preparation method thereof, and is characterized in that: the general formula of the sodium vanadium phosphate positive electrode material is Na 3 V 2-x M x (PO 4-y ) 3 Y 3y /C, wherein 0<x≤0.2, 0<y≤0.05, M is Al, Fe, Cr, Ni, Co, Mg, Zn, La, Cu, Mn, Ti, Mo, Sn, Sr, Nb , Ce or Y, Y is F or Cl. The invention improves the electronic conductivity of the material and significantly improves the electrochemical performance of the material by carrying out carbon coating and anion-cation co-doping modification on the sodium vanadium phosphate positive electrode material.
Description
Technical field
The present invention relates to a kind of preparation method of sodium-ion battery positive material more particularly to a kind of zwitterion doped carbons
Coat the preparation method of vanadium phosphate sodium positive electrode
Background technique
Lithium ion battery is because have specific energy is high, have extended cycle life, charge power range is wide, multiplying power discharging property is good etc.
Advantage is widely used in the various portable electronic products such as laptop, mobile phone, digital camera and instrument and equipment.With
The fast development of portable electronic product and electric car, the demand to lithium ion battery is more more and more urgent, and the demand of lithium will
It can greatly increase.The ratio of elemental lithium is about 0.0065% in the earth's crust, and abundance occupies the 27th in various elements.Lithium metal is high
High cost makes people have to set about seeking inexpensive lithium battery system substitute.
Sodium rich reserves, low in cost for lithium, the abundance in the earth's crust is up to 2.64%.And sodium and lithium are of the same clan, change
It is similar to learn property, therefore sodium-ion battery receives the favor of researchers.The wherein Na of NASICON structure3V2(PO4)3It obtains
The extensive concern of researchers.Na3V2(PO4)3With three-dimensional frame structure, facilitate the insertion and abjection of sodium ion, and embedding
It is smaller on the influence of the volume change of material to enter abjection process, so that material has preferable circulation and high rate performance.But with
LiFePO4Equally, Na3V2(PO4)3There are electron conductions it is poor, ion diffusivity is small the disadvantages of, to affect its electrochemistry
Performance.Therefore need to be doped it coating modification research, to promote its chemical property.
Summary of the invention
The present invention is to provide a kind of zwitterion doping carbon coating to avoid above-mentioned existing deficiencies in the technology
Vanadium phosphate sodium positive electrode and preparation method thereof, it is intended to improve existing Na3V2(PO4)3Performance.
The general formula of zwitterion doping carbon coating vanadium phosphate sodium positive electrode of the invention is Na3V2-xMx(PO4-y)3Y3y/ C,
0 x≤0.2 <, 0 < y≤0.05, M Al, Fe, Cr, Ni, Co, Mg, Zn, La, Cu, Mn, Ti, Mo, Sn, Sr, Nb, Ce or Y, Y
For F or Cl.Preparation method includes the following steps:
(1) sodium source, vanadium source, the source M, phosphorus source, the source Y are weighed according to the molar ratio of Na:V:M:P:Y:C=3:2-x:x:3:3y:2
And carbon source；
(2) carbon source, vanadium source, the source M and the source Y are mixed, deionized water is added, stirring adds under 70 DEG C~90 DEG C water bath conditions
0.5~1.5h of heat forms mixed liquor；Then by phosphorus source and sodium source it is miscible after, instilled in the mixed liquor dropwise, lasting stirring plus
Heat forms gel；After gel vacuum drying, grinding obtains mixed-powder；
(3) by the mixed-powder full of inert gas tube furnace in, with 300 DEG C~400 DEG C low temperature just burn 3~
4h, products therefrom regrind uniform after taking out；Then again in the tube furnace full of inert gas, with 700 DEG C~900 DEG C height
Temperature 7~12h of calcining, i.e. acquisition zwitterion adulterate carbon coating vanadium phosphate sodium positive electrode.
Preferably, the carbon source is at least one of citric acid, glucose, oxalic acid and polyvinyl alcohol.
Preferably, the sodium source is at least one of sodium carbonate, sodium hydroxide and disodium hydrogen phosphate.
Preferably, the vanadium source is at least one of ammonium metavanadate and vanadic anhydride.
Preferably, phosphorus source is at least one of ammonium di-hydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate.
Preferably, the source M is at least one of nitrate, sulfate and acetate containing M.
Preferably, the source Y is at least one of ammonium fluoride, sodium fluoride, ammonium chloride and sodium chloride.
Preferably, the heating rate that low temperature described in step (3) is just burnt is 2-5min/ DEG C, the heating of the high-temperature calcination
Rate is 1-2min/ DEG C.
Preferably, inert gas described in step (3) is nitrogen or argon gas.
Compared with the prior art, the beneficial effects of the present invention are embodied in:
1, the present invention improves material by carrying out carbon coating and the miscellaneous modification of cation-anion co-doping to vanadium phosphate sodium positive electrode
The electronic conductivity of material, and significantly improve the chemical property of material.
2, the present invention adulterates carbon coating phosphoric acid by collosol and gel and the method for calcining combination twice, the zwitterion of preparation
Vanadium sodium positive electrode, carbon layer on surface is uniform, and zwitterion has not been changed crystal structure, generates lattice defect, facilitates sodium ion
Deintercalation and insertion, significantly improve chemical property.
Detailed description of the invention
Fig. 1 is the embodiment of the present invention 1, embodiment 2, the XRD diagram of vanadium phosphate sodium positive electrode prepared by embodiment 3；
Fig. 2 is the charge and discharge for the first time of the embodiment of the present invention 1, embodiment 2, vanadium phosphate sodium positive electrode prepared by embodiment 3
Electric curve graph；
Fig. 3 be the embodiment of the present invention 1, embodiment 2, vanadium phosphate sodium positive electrode prepared by embodiment 3 high rate performance figure.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings and specific examples.
Embodiment 1
The present embodiment prepares vanadium phosphate sodium positive electrode Na as follows3V2(PO4)3/ C:
(1) sodium carbonate 0.3975g, ammonium metavanadate 0.5849g, phosphorus are weighed according to the molar ratio of Na:V:P:C=3:2:3:2
Acid dihydride ammonia 0.8627g, citric acid 1.0507g；
(2) citric acid and ammonium metavanadate are mixed, 200mL deionized water, the agitating and heating under 80 DEG C of water bath conditions is added
1h forms mixed liquor；Then by sodium carbonate and ammonium di-hydrogen phosphate it is miscible in deionized water after, dropwise instill mixed liquor in, hold
Continuous agitating and heating 4h, forms gel；After gel is dried in vacuo, grinding obtains mixed-powder；
(3) mixed-powder is warming up to 350 DEG C of heat preservation 4h, products therefrom by 2min/ DEG C in the tube furnace full of nitrogen
It is regrind after taking-up uniform；Then 850 DEG C of heat preservation 8h are warming up to by 1 DEG C/min, that is, are obtained in the tube furnace full of nitrogen again
Obtain carbon coating vanadium phosphate sodium positive electrode.
Carbon coating vanadium phosphate sodium positive electrode manufactured in the present embodiment is subjected to X-ray diffraction test, as shown in Figure 1, can
It is consistent with standard card with the vanadium phosphate sodium for finding out prepared.
Chemical property of the gained sample as positive electrode is tested as follows:
7:2:1 in mass ratio weighs carbon coating vanadium phosphate sodium positive electrode manufactured in the present embodiment and acetylene black, gathers inclined fluorine
Cathode film is made in ethylene, and film thickness is 20 μm, rolls punching, obtains positive plate；Using metal lithium sheet as cathode, with glass fibre (GF/
It D) is diaphragm, the NaClO with 1mol/L4(PC) it is electrolyte, 2032 type button cells is assembled into glove box.
Assembled battery is subjected to charge-discharge performance test at room temperature, voltage range is 2.5~3.8V.For the first time
Charging and discharging curve such as Fig. 2, first discharge specific capacity of the material at 0.5C are 104.5mAhg-1, 100 times circulation after discharge hold
Amount is 82.85mAhg-1, capacity retention ratio 79%.Discharge capacity under 1C, 2C multiplying power is 98.02mAhg-1,
84.26mAhg-1.It can be seen that the positive electrode stability that the present embodiment obtains is bad.Its high rate performance such as Fig. 3, high rate performance compared with
Difference needs to be doped it research.
Embodiment 2
The present embodiment prepares cobalt doped carbon coating vanadium phosphate sodium positive electrode Na as follows3V1.9Co0.1(PO4)3/ C:
(1) sodium carbonate 0.3975g, ammonium metavanadate are weighed according to the molar ratio of Na:V:Co:P:C=3:1.9:0.1:3:2
0.5557g, cobalt nitrate 0.0728g, ammonium di-hydrogen phosphate 0.8627g, citric acid 1.0507g；
(2) citric acid, ammonium metavanadate and cobalt nitrate are mixed, 200mL deionized water is added, is stirred under 80 DEG C of water bath conditions
Heating 1h is mixed, mixed liquor is formed；Then by sodium carbonate and ammonium di-hydrogen phosphate it is miscible in deionized water after, instill mixed liquor dropwise
In, continue agitating and heating 4h, forms gel；After gel is dried in vacuo, grinding obtains mixed-powder；
(3) mixed-powder is warming up to 350 DEG C of heat preservation 4h, products therefrom by 2min/ DEG C in the tube furnace full of nitrogen
It is regrind after taking-up uniform；Then 850 DEG C of heat preservation 8h are warming up to by 1 DEG C/min, that is, are obtained in the tube furnace full of nitrogen again
Obtain cobalt doped carbon coating vanadium phosphate sodium positive electrode.
Cobalt doped carbon coating vanadium phosphate sodium positive electrode manufactured in the present embodiment is subjected to X-ray diffraction test, such as Fig. 1 institute
Show, compareed with standard card, determines that there is no change vanadium phosphate sodium crystal structure for cationic cobalt doping.
Chemical property of the gained sample as positive electrode is tested as follows:
7:2:1 in mass ratio weigh cobalt doped carbon coating vanadium phosphate sodium positive electrode manufactured in the present embodiment and acetylene black,
Cathode film is made in Kynoar, and film thickness is 20 μm, rolls punching, obtains positive plate；Using metal lithium sheet as cathode, with glass fibers
Tieing up (GF/D) is diaphragm, the NaClO with 1mol/L4(PC) it is electrolyte, 2032 type button cells is assembled into glove box.
Assembled battery is subjected to charge-discharge performance test at room temperature, voltage range is 2.5~3.8V.For the first time
Charging and discharging curve such as Fig. 2, first discharge specific capacity of the material at 0.5C are 106.4mAhg-1, 100 times circulation after discharge hold
Amount is 95.16mAhg-1, capacity retention ratio 89.4%, it is seen that discharge capacity for the first time and capacity retention ratio after doping are mentioned
It is high.Its high rate performance such as Fig. 3, it is seen that high rate performance is also improved after doping.
Embodiment 3
The present embodiment prepares the fluorin-doped carbon coating vanadium phosphate sodium positive electrode Na of cobalt as follows3V1.9Co0.1
(PO3.99)3F0.03/ C:
(1) according to the molar ratio of Na:V:Co:P:F:C=3:1.90:0.1:3:0.03:2 weigh sodium carbonate 0.3935g, partially
Ammonium vanadate 0.5557g, cobalt nitrate 0.0728g, ammonium di-hydrogen phosphate 0.8627g, sodium fluoride 0.0031g, citric acid 1.0507g；
(2) citric acid, ammonium metavanadate, cobalt nitrate and sodium fluoride are mixed, 200mL deionized water is added, in 80 DEG C of water-baths
Under the conditions of agitating and heating 1h, formed mixed liquor；Then by sodium carbonate and ammonium di-hydrogen phosphate it is miscible in deionized water after, drip dropwise
Enter in mixed liquor, continue agitating and heating 4h, forms gel；After gel is dried in vacuo, grinding obtains mixed-powder；
(3) mixed-powder is warming up to 350 DEG C of heat preservation 4h, products therefrom by 2min/ DEG C in the tube furnace full of nitrogen
It is regrind after taking-up uniform；Then 850 DEG C of heat preservation 8h are warming up to by 1 DEG C/min, that is, are obtained in the tube furnace full of nitrogen again
Obtain the fluorin-doped carbon coating vanadium phosphate sodium positive electrode of cobalt.
The fluorin-doped carbon coating vanadium phosphate sodium positive electrode of cobalt manufactured in the present embodiment is subjected to X-ray diffraction test, such as
It shown in Fig. 1, is compareed with standard card, determines that cation-anion co-doping is miscellaneous and do not change vanadium phosphate sodium crystal structure.
Chemical property of the gained sample as positive electrode is tested as follows:
7:2:1 in mass ratio weighs the fluorin-doped carbon coating vanadium phosphate sodium positive electrode of cobalt manufactured in the present embodiment and acetylene
Cathode film is made in black, Kynoar, and film thickness is 20 μm, rolls punching, obtains positive plate；Using metal lithium sheet as cathode, with glass
Glass fiber (GF/D) is diaphragm, the NaClO with 1mol/L4(PC) it is electrolyte, 2032 type button electricity is assembled into glove box
Pond.
Assembled battery is subjected to charge-discharge performance test at room temperature, voltage range is 2.5~3.8V.For the first time
Charging and discharging curve such as Fig. 2, first discharge specific capacity of the material at 0.5C are 110.4mAhg-1, 100 times circulation after discharge hold
Amount is 102.36mAhg-1, capacity retention ratio 92.7%, it is seen that the discharge capacity for the first time after codope is compared with capacity retention ratio
It is all improved in independent cation doping or the sample that undopes.The high rate performance of the material such as Fig. 3, the electric discharge at 1C, 2C
Capacity is 105.33mAhg-1, 92.58mAhg-1, high rate performance, which is similarly obtained, to be significantly improved.
Claims (9)
1. a kind of preparation method of zwitterion doping carbon coating vanadium phosphate sodium positive electrode, it is characterised in that: the yin-yang from
The general formula of son doping carbon coating vanadium phosphate sodium positive electrode is Na3V2-xMx(PO4-y)3Y3y/ C, wherein 0 x≤0.2 <, 0 < y≤
0.05, M Al, Fe, Cr, Ni, Co, Mg, Zn, La, Cu, Mn, Ti, Mo, Sn, Sr, Nb, Ce or Y, Y are F or Cl；
The preparation method of the zwitterion doping carbon coating vanadium phosphate sodium positive electrode, includes the following steps:
(1) sodium source, vanadium source, the source M, phosphorus source, the source Y and carbon are weighed according to the molar ratio of Na:V:M:P:Y:C=3:2-x:x:3:3y:2
Source；
(2) carbon source, vanadium source, the source M and the source Y are mixed, deionized water, the agitating and heating under 70 DEG C~90 DEG C water bath conditions is added
0.5~1.5h forms mixed liquor；Then by phosphorus source and sodium source it is miscible after, instilled in the mixed liquor dropwise, lasting stirring plus
Heat forms gel；After gel vacuum drying, grinding obtains mixed-powder；
(3) by the mixed-powder in the tube furnace full of inert gas, 3~4h, institute are just burnt with 300 DEG C~400 DEG C low temperature
It obtains after product takes out and regrinds uniformly；Then it is forged again in the tube furnace full of inert gas with 700 DEG C~900 DEG C high temperature
7~12h is burnt, i.e. acquisition zwitterion adulterates carbon coating vanadium phosphate sodium positive electrode.
2. the preparation method of zwitterion doping carbon coating vanadium phosphate sodium positive electrode according to claim 1, feature
Be: the carbon source is at least one of citric acid, glucose, oxalic acid and polyvinyl alcohol.
3. the preparation method of zwitterion doping carbon coating vanadium phosphate sodium positive electrode according to claim 1, feature
Be: the sodium source is at least one of sodium carbonate, sodium hydroxide and disodium hydrogen phosphate.
4. the preparation method of zwitterion doping carbon coating vanadium phosphate sodium positive electrode according to claim 1, feature
Be: the vanadium source is at least one of ammonium metavanadate and vanadic anhydride.
5. the preparation method of zwitterion doping carbon coating vanadium phosphate sodium positive electrode according to claim 1, feature
Be: phosphorus source is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate.
6. the preparation method of zwitterion doping carbon coating vanadium phosphate sodium positive electrode according to claim 1, feature
Be: the source M is at least one of nitrate, sulfate and acetate containing M.
7. the preparation method of zwitterion doping carbon coating vanadium phosphate sodium positive electrode according to claim 1, feature
Be: the source Y is at least one of ammonium fluoride, sodium fluoride, ammonium chloride and sodium chloride.
8. the preparation method of zwitterion doping carbon coating vanadium phosphate sodium positive electrode according to claim 1, feature
Be: the heating rate that low temperature described in step (3) is just burnt is 2-5min/ DEG C, and the heating rate of the high-temperature calcination is 1-
2min/℃。
9. the preparation method of zwitterion doping carbon coating vanadium phosphate sodium positive electrode according to claim 1, feature
Be: inert gas described in step (3) is nitrogen or argon gas.
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